Polymeric compositions for forming optical waveguides; optical waveguides formed therefrom; and methods for making same

ABSTRACT

The present invention relates to polymer compositions and methods of polymerizing such compositions. Furthermore, the present invention relates to polymer compositions that are useful in forming waveguides and to methods for making waveguides using such polymer compositions.

RELATED APPLICATION DATA

This application claims priority to previously filed U.S. ProvisionalApplication No. 60/221,420, filed on Jul. 28, 2000, entitled “PolymericCompositions for Forming Optical Waveguides; Optical Waveguides FormedTherefrom; and Methods for Making Same”, and U.S. ProvisionalApplication No. 60/252,251, filed on Nov. 21, 2000 entitled “PolymericCompositions for Forming Optical Waveguides; Optical Waveguides FormedTherefrom; and Methods for Making Same”, both of which are incorporatedherein by reference in their entireties.

FIELD OF THE INVENTION

The invention herein described relates generally to polymericcompositions for forming optical waveguides and methods for forming suchoptical waveguides using the same. In particular, the present inventionrelates to polymers made from at least one cyclic olefin monomer whichcan be used to form optical waveguides using either a clad-first or corefirst technique.

BACKGROUND OF THE INVENTION

The demand for continuous increase in transmission speed, data capacityand data density in integrated optical and optoelectronic circuits hasbeen the motivating force behind numerous innovations in areas ofbroadband communications, high-capacity information storage, and largescreen and portable information display. Although glass optical fibersare routinely used for high-speed data transfer over long distances,they are inconvenient for complex high-density circuitry because oftheir high density, poor durability and high cost of fabrication forcomplex photonic circuits. As such, polymeric materials hold greatpromise for constructing cost effective, reliable, passive and activeintegrated components capable of performing the required functions forintegrated optics.

SUMMARY OF THE INVENTION

The present invention relates generally to polymeric compositions forforming optical waveguides and methods for forming such opticalwaveguides using the same. In particular, the present invention relatesto polymers made from at least one cyclic olefin monomer which can beused to form optical waveguides using either a clad-first or core firsttechnique.

In one embodiment, the present invention relates to polycyclic polymercompositions formed from one or more monomers or oligomers representedby the following structure:

wherein each X′″ independently represents oxygen, nitrogen, sulfur, or amethylene group of the formula —(CH₂)_(n′)— where n′ is an integer of 1to 5; “a” represents a single or double bond; R¹ to R⁴ independentlyrepresent a hydrogen, a hydrocarbyl, or a functional substituent; and mis an integer from 0 to 5, with the proviso that when “a” is a doublebond one of R¹, R² and one of R³, R⁴ are not present.

In another embodiment, R¹ to R⁴ independently comprises a hydrocarbyl, ahalogenated hydrocarbyl or a perhalogenated hydrocarbyl group which areselected from: i) linear or branched C₁-C₁₀ alkyl groups; ii) linear orbranched C₂-C₁₀ alkenyl groups; iii) linear or branched C₂-C₁₀ alkynylgroups; iv) C₄-C₁₂ cycloalkyl groups; v) C₄-C₁₂ cycloalkenyl groups; vi)C₆-C₁₂ aryl groups; and vii) C₇-C₂₄ aralkyl groups, provided that atleast one of R¹ to R⁴ is a hydrocarbyl group.

In another embodiment, one or more of R¹ to R⁴ represent a functionalsubstituent independently selected from —(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃,—(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—CH₃, —(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(CH₃),—(CH₂)_(n)—C(CF₃)₂—OH, —(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl,—(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵, —(CH₂)_(n)—OC(O)R⁵,—(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵, —(CH₂)_(n)Si(R⁵)₃,—(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)—O—Si(R⁵)₃, and —(CH₂)_(n)C(O)OR⁶ where inindependently represents an integer from 0 to 10, R⁵ independetylrepresents a hydrogen, a linear or branched C₁-C₂₀ alkyl group, a linearor branched C₁-C₂₀ halogenated or perhalogenated alkyl group, a linearor branched C₂-C₁₀ alkenyl group, a linear or branched C₂-C₁₀ alkynylgroup, a C₅-C₁₂ cycloalkyl group, a C₆-C₁₄ aryl group, a C₆-C₁₄halogenated or perhalogenated aryl group and a C₇-C₂₄ aralkyl group; andR⁶ is selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃, —CH(R⁷)OC(CH₃)₃or one of the following cyclic groups:

or one of the following:

wherein R⁷ represents a hydrogen or a linear or branched (C₁-C₅) alkylgroup.

In still another embodiment, a polymer composition in accordance withthe present invention is formed from one or more monomers or oligomersas described herein in combination with one or more crosslinking agents.Furthermore, in still another embodiment, the one or more crosslinkingagents are latent crosslinking agents.

In one embodiment, the at least one crosslinking agent can be thecompound shown below:

In yet another embodiment, the one or more crosslinking agents arerepresented by one or more of the following structures:

In yet another embodiment, the present invention relates to polycyclicpolymer compositions formed from one or more monomers or oligomersrepresented by the following structure:

wherein each X′″ independently represents oxygen, nitrogen, sulfur, or amethylene group of the formula —(CH₂)_(n′)— where n′ is an integer of 1to 5; Q represents an oxygen atom or the group N(R⁸); R⁸ is selectedfrom hydrogen, a halogen, a linear or branched C₁-C₁₀ alkyl, and C₆-C₁₈aryl; and m is an integer from 0 to 5.

In yet another embodiment, a polycyclic polymer composition formed fromone or more monomers represented by the following structure:

wherein X′″ represents oxygen, nitrogen, sulfur, or a methylene group ofthe formula —(CH₂)_(n′)— where n′ is an integer of 1 to 5; R^(D) isdeuterium, “i” is an integer ranging from 0 to 6, with the proviso thatwhen “i” is 0, at least one of R^(1D) and R^(2D)must be present; R¹ andR² independently represent a hydrogen, a hydrocarbyl, or a functionalsubstituent; and R^(1D) and R^(2D), which are optional, independentlyrepresent a deuterium atom or a deuterium enriched hydrocarbyl groupcontaining at least one deuterium atom.

In another embodiment, a polymer composition for use in a waveguide isproduced from one or more monomers or oligomers described.

In still another embodiment, a polymer composition according to thepresent invention further includes at least one crosslinking agent. Inone embodiment, the crosslinking agent is a latent crosslinking agent.

The present invention is advantageous in that it provides polymercompositions which permit the formation of optical waveguides havingbetter performance qualities such as, for example, a difference (Δn) inthe refractive index of the core material versus that of the cladmaterial of at least about 0.00075 (i.e., at least about 0.05% where theclad or cladding material has a refractive index of about 1.5) for overa broad wavelength range (e.g., about 400 to about 1600 nm); lowerintrinsic optical loss (lower than about 1 dB/cm and in some cases lowerthan about 0.5 dB/cm); a high glass transition temperature (Tg) (e.g.,in one embodiment at least about 150° C., in another embodiment at leastabout 250° C., and in some cases at least about 280° C.).

Additionally, the present invention is advantageous in that it providescore and/or cladding compositions which can have a low viscosity orviscosities so as to be deliverable by any suitable technique, includingink jet printers, screen printers or stencil printers. Furthermore, thedisclosed core-first method for forming optical waveguides isadvantageous in that it permits the formation of optical waveguides witha reduction and/or elimination in the occurrence of “swelling” betweenlayers (see FIGS. 5A and 5B for a photographic depiction of “swelling”).Thus, the core-first method permits the formation of improvedwaveguides.

The foregoing and other features of the invention are hereinafter fullydescribed and particularly pointed out in the claims, the followingdescription and the annexed drawings setting forth in detail one or moreillustrative embodiments of the invention, such being indicative,however, of but one or a few of the various ways in which the principlesof the invention may be employed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a step diagram of the steps of a clad-first waveguideformation method;

FIGS. 2A to 2C depict waveguide structures formed using the clad-firstmethod of FIG. 1;

FIG. 3 is a step diagram of the steps of a core-first waveguideformation method of the present invention;

FIGS. 4A to 4D are another set of waveguides formed using the core-firstmethod of the present invention;

FIGS. 5A and 5B are photographs comparing the clad-first waveguideforming method of FIG. 1 to the core-first waveguide forming method ofFIG. 3;

FIG. 6 is a step diagram of the steps of a modified core-first waveguideformation method of the present invention;

FIGS. 7A and 7B are optical micrographs depicting a waveguide formed inaccordance with the methods of FIGS. 3 and 6, respectively;

FIG. 8 is a step diagram of the steps of a method for formingisolate-buried channel waveguides by cutting multi-layer films; and

FIGS. 9A to 9D depict waveguide structure formed using the multilayermethod of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

As stated above, the present invention relates to a variety of methodswhich can be used to form optical waveguides, and more specifically toform optical waveguides having buried channels. Also, the presentinvention relates to compositions which can be used to form opticalwaveguides.

It should be noted that in the following text and claims, range andratio limits and/or range and time limits may be combined. Additionally,as used throughout the specification and claims the terms corecomposition and cladding (or clad) composition are defined to mean oneof the following:

(1) a composition which includes at least one monomer;

(2) a composition which includes at least one monomer and at least oneoligomer, where the total amount of reactive monomer and/or reactiveoligomer is at least about 30 weight percent based on the total weightof either the core or cladding composition;

(3) a composition which includes at least one monomer and at least onepolymer, where the total amount of reactive monomer is at least about 30weight percent based on the total weight of either the core or claddingcomposition; and

(4) a composition which includes at least one monomer, at least oneoligomer and at least one polymer, where the total amount of reactivemonomer and/or reactive oligomer is at least about 30 weight percentbased on the total weight of either the core or cladding composition.Oligomer as used throughout the specification and claims is defined tomean a composition containing less than about 1000 repeating units of agiven monomer.

Furthermore, the refractive indices referred to herein were measuredusing an Abbe refractometer at 589 nm and/or a Metricon Model 2010 prismcoupler at 633 nm, 830 nm, and 1550 nm, following the guideline of ASTMDesignation #D542-95.

Generally, optical waveguides and even buried channel optical waveguidesare composed of a core layer having a first index of refraction and acladding layer having a second index of refraction, wherein the corelayer is at least partially encompassed by the cladding layer. Inanother embodiment, the core layer is completely encompassed by thecladding layer (i.e., a buried channel structure or three-layer opticalwaveguide). It is the core which transmits light and the cladding layerwhich confines light. In the situation where the optical waveguide is atwo layer structure, the core layer is partially bound by a layer ofair.

In view of the above, formulations for each of the core and cladding (orclad) layers will be discussed below. However, in the general sense themethods disclosed below will work with any suitable polymer or polymersso long as the resulting core and cladding (or clad) layers formedtherefrom meet the necessary performance criteria for the application inwhich the waveguide will be utilized. Numerous waveguide performancecriteria exist, Table 1 summarizes the general minimum performancecriteria which are applicable to all waveguides irrespective of thewaveguide application. It should be noted though, that the presentinvention is not limited thereto. Rather, based on the polymer orpolymers utilized, other performance criteria are obtainable.

TABLE I Comparative Performance of a Waveguide Using the CoreComposition of Example CL5 and the Performance Minimum CladdingComposition Criteria Requirement of Example CO1 Refractive Index at atleast about about 0.03 (about 830 nm Δn (core- 0.00075 (which 2.0% wherethe clad clad): corresponds to about refractive index is 0.05% where theapproximately 1.5) clad refractive index is approximately 1.5) ΔnConsistent Over about 0 to about 0 to 175° C. a Broad Temp. 40° C.Range: Intrinsic Optical less than about 1 less than about 0.1 dB/ Loss:dB/cm cm (at 515 to 870 nm) Transmission Loss less than about 1 about0.14 dB/cm of Waveguide: dB/cm Birefringence, both less than about 10⁻²/less than about 10⁻⁵/ In-Plane/Out-Of- less than about 10⁻² less thanabout 10⁻³ Plane (Δn): Oxidative Stability at least 500 hours at atleast about 2200 is 2000 hours at 125° C. hours at 125° C. 125° C. inair Solder Reflow Tg is at least Tg is at least 250° C. Compatible Dueto a 150° C. Minimum Glass Transition Temp. (Tg): Low Moisture less thanabout 3% less than about 0.3% Absorption: Mechanically at least about 5%at least about 10% Robust Due to a Minimum Elongation:

In one embodiment, waveguides can be formed via the methods discussedbelow by using a variety of polymer compounds, such compounds include,but are not limited to, polyacrylates (such as deuteratedpolyfluoromethacrylate), polyimides (such as cross-linked polyimides orfluorinated polyimides), benzocyclobutene or fluorinatedbenzocyclobutene.

In another embodiment, the waveguides of the present invention areformed from polymers formed from cyclic olefin monomers. In yet anotherembodiment, the cyclic olefin monomers used to form the waveguidepolymers are norbornene-type monomers.

Formation of Cyclic Olefin Polymers

In general, the polymerization of the cycloolefins used in oneembodiment of the present invention are, in one embodiment, conductedusing a Group 10 metal complex via addition polymerization to yieldsaturated, high glass transition temperature polymers. In anotherembodiment, the polymerization of the cycloolefins used in oneembodiment of the present invention are conducted using a Group 10 metalcomplex and a weakly coordinating counteranion.

In yet another embodiment, the cycloolefins are polymerized bycontacting a polymerizable polycycloolefin monomer charge with a highactivity catalyst system comprising a Group 10 metal cation complex anda weakly coordinating counteranion complex of the formula:

[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)

wherein M represents a Group 10 transition metal; R¹ represents ananionic hydrocarbyl containing ligand; L′ represents a Group 15 neutralelectron donor ligand; L″ represents a labile neutral electron donorligand; z is 0 or 1; x is 1 or 2; y is 0, 1, 2, or 3, and the sum of x,y, and z equals 4; and b and d are numbers representing the number oftimes the cation complex and weakly coordinating counteranion complex(WCA), respectively, are taken to balance the electronic charge on theoverall catalyst complex. The monomer charge can be neat or in solution,and is contacted with a preformed catalyst of the foregoing formula.Alternatively, the catalyst can be formed in situ by admixing thecatalyst forming components in the monomer charge.

Catalyst System

The catalyst of the invention comprises a Group 10 metal cation complexand a weakly coordinating counteranion complex represented by Formula Ibelow:

[(R′)_(z)M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  I

wherein M represents a Group 10 transition metal; R¹ represents ananionic hydrocarbyl ligand; L′ represents a Group 15 neutral electrondonor ligand; L″ represents a labile neutral electron donor ligand; x is1 or 2; y is 0, 1, 2, or 3, wherein the sum of x, y, and z is 4; and band d are numbers representing the number of times the cation complexand weakly coordinating counteranion complex (WCA), respectively, aretaken to balance the electronic charge of the overall catalyst complex.

The weakly coordinating counteranion complex is an anion which is onlyweakly coordinated to the cation complex. It is sufficiently labile tobe displaced by a neutral Lewis base, solvent or monomer. Morespecifically, the WCA anion functions as a stabilizing anion to thecation complex and does not transfer to the cation complex to form aneutral product. The WCA anion is relatively inert in that it isnon-oxidative, non-reducing, and non-nucleophilic.

An anionic hydrocarbyl ligand is any hydrocarbyl ligand which whenremoved from the metal center M in its closed shell electronconfiguration, has a negative charge.

A neutral electron donor is any ligand which when removed from the metalcenter M in its closed shell electron configuration, has a neutralcharge.

A labile neutral electron donor ligand is any ligand which is not asstrongly bound to metal center M, is easily displaced therefrom, andwhen removed from the metal center in its closed shell electronconfiguration has a neutral charge.

In the cation complex above, M represents a Group 10 metal selected fromnickel, palladium. In another embodiment, M represents platinum.

Representative anionic hydrocarbyl containing ligands defined under R′include hydrogen, linear or branched C₁-₂₀ alkyl, C₅-C₁₀ cycloalkyl,linear or branched C₂-C₂₀ alkenyl, C₆-C₁₅ cycloalkenyl, allylic ligandsor canonical forms thereof, C₆-C₃₀ aryl, C₆-C₃₀ heteroatom containingaryl, and C₇-C₃₀ aralkyl, each of the foregoing groups can be optionallysubstituted with hydrocarbyl and/or heteroatom substituents which, inone embodiment, are selected from linear or branched C₁-C₅ alkyl, linearor branched C₁-C₅ haloalkyl, linear or branched C₂-C₅ alkenyl andhaloalkenyl, halogen, sulfur, oxygen, nitrogen, phosphorus, and phenyloptionally substituted with linear or branched C₁-₅ alkyl, linear orbranched C₁-C₅ haloalkyl, and halogen, R′ also represents anionichydrocarbyl containing ligands of the formula R″C(O)O, R″OC(O)CHC(O)R″,R″C(O)S, R″C(S)O, R″C(S)S, R″O, R″₂N, wherein R″ is the same as R′defined immediately above.

The foregoing cycloalkyl, and cycloalkenyl ligands can be monocyclic ormulticyclic. The aryl ligands can be a single ring (e.g., phenyl) or afused ring system (e.g., naphthyl). In addition, any of the cycloalkyl,cycloalkenyl and aryl groups can be taken together to form a fused ringsystem. Each of the monocyclic, multicyclic and aryl ring systemsdescribed above optionally can be monosubstituted or multisubstitutedwith a substituent independently selected from hydrogen, linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, halogen selected from chlorine, fluorine, iodineand bromine, C₅-C₁₀ cycloalkyl, C₆-C₁₅ cycloalkenyl, and C₆-C₃₀ aryl. Anexample of a multicycloalkyl moiety is a norbornyl ligand. An example ofa multicycloalkenyl moiety is a norbornenyl ligand. Examples of arylligand groups include phenyl and naphthyl. For purposes of illustrationStructure I below represents a cationic complex wherein R′ is acycloalkenyl ligand derived from 1,5-cyclooctadiene. Structures II andIII illustrate cationic complexes wherein R′ represents multicycloalkyland multicycloalkenyl ligands, respectively. In Structure III thenorbornenyl ligand is substituted with an alkenyl group.

wherein M, L′, L″, x and y are as previously defined.

Additional examples of cationic complexes where R′ represents a ringsystem is illustrated in Structures IV to IVc below.

wherein M, L′, L″, x and y are as previously defined.

In another embodiment of the invention R′ represents a hydrocarbylligand containing a terminal group that coordinates to the Group 10metal. The terminal coordination group containing hydrocarbyl ligand arerepresented by the formula —C_(d′)H_(2d′)X→, wherein d′ represents thenumber of carbon atoms in the hydrocarbyl backbone and is an integerfrom 3 to 10, and X→ represents an alkenyl or heteroatom containingmoiety that coordinates to the Group 10 metal center. The ligandtogether with the Group 10 metal forms a metallacycle or heteroatomcontaining metallacycle. Any of the hydrogen atoms on the hydrocarbylbackbone in the formulae above can be independently replaced by asubstituent selected from R^(1′), R^(2′), and R^(3′) which are definedbelow.

A cation complex of the terminal coordination group containinghydrocarbyl metallacycle embodiment is represented by Structure V shownbelow:

wherein M, L′, L″, d′, x and y are as previously defined, and Xrepresents a radical selected from the group —CHR^(4′)═CHR^(4′),—OR^(4′), —SR^(4′), —N(R^(4′))₂, —N═NR^(4′), —P(R^(4′))₂, —C(O)R^(4′),—C(R^(4′))═NR^(4′), —C(O)OR^(4′), —OC(O)OR^(4′), —OC(O)R^(4′), andR^(4′) represents hydrogen, halogen, linear or branched C₁-C₅ alkyl,linear or branched C₁-C₅ haloalkyl, C₅-C₁₀ cycloalkyl, linear orbranched C₂-C₅ alkenyl, linear or branched C₂-C₅ haloalkenyl,substituted and unsubstituted C₆-C₁₈ aryl, and substituted andunsubstituted C₇-C₂₄ aralkyl.

The substituted terminal group containing hydrocarbyl metallacycles canbe represented by structure Va, below.

wherein M, L′, L″, X, x and y are as previously defined, n represents aninteger from 0 to 8 and R^(1′), R^(2′), and R^(3′) independentlyrepresent hydrogen, linear or branched C₁-C₅ alkyl, linear or branchedC₁-C₅ haloalkyl, linear or branched C₂-C₅ alkenyl, linear or branchedC₂-C₅ haloalkenyl, substituted and unsubstituted C₆-C₃₀ aryl,substituted and unsubstituted C₇-C₃₀ aralkyl, and halogen. Any ofR^(1′), R^(2′), and R^(3′) can be taken together along with the carbonatoms to which they are attached can form a substituted or unsubstitutedaliphatic C₅-C₂₀ monocyclic or polycyclic ring system, a substituted orunsubstituted C₆-C₁₀ aromatic ring system, a substituted andunsubstituted C₁₀-C₂₀ fused aromatic ring system, and combinationsthereof. When substituted, the rings described above can containmonosubstitution or multisubstitution where the substituents areindependently selected from hydrogen, linear or branched C₁-₅ alkyl,linear or branched C₁-₅ haloalkyl, linear or branched C₁-₅ alkoxy, andhalogen selected from chlorine, fluorine, iodine and bromine. InStructure Va above it should be noted that when n is 0, X is bonded tothe carbon atom that contains the R^(2′) substituent.

Representative terminal group containing hydrocarbyl metallacycle cationcomplexes wherein the substituents are taken together to representaromatic and aliphatic ring systems are illustrated below underStructures Vb and Vc.

Additional examples of terminal group containing hydrocarbylmetallacycle cation complexes wherein any of R^(1′) to R^(3′) can betaken together to form aromatic ring systems are set forth in StructuresVd to Vg below.

Illustrative examples of cation complexes containing polycyclicaliphatic ring systems are set forth under structures Vh, Vi, and Vjbelow:

In Structures V through Vj above, n′ is an integer from 0 to 5; and X,M, L′, L″, n, x, y, R^(1′) and R^(4′), are as previously defined, and“a” represents a single or double bond, R^(5′) and R^(6′) independentlyrepresent hydrogen, and linear or branched C₁-C₁₀ alkyl, R^(5′) andR^(6′) together with the carbon atoms to which they are attached canform a saturated and unsaturated cyclic group containing 5 to 15 carbonatoms.

Examples of heteroatom containing aryl ligands under R′ are pyridinyland quinolinyl ligands.

The allyl ligand in the cationic complex can be represented by thefollowing structure:

wherein R^(20′), R^(21′), and R^(22′) each independently representhydrogen, halogen, linear or branched C₁-C₅ alkyl, C₅-C₁₀ cycloalkyl,linear or branched C₁-C₅ alkenyl, C₆-C₃₀ aryl, C₇-C₃₀ aralkyl, eachoptionally substituted with a substituent selected from linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, halogen, andphenyl which can optionally be substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, and halogen. Any two ofR^(20′), R^(21′), and R^(22′) can be linked together with the carbonatoms to which they are attached to form a cyclic or multicyclic ring,each optionally substituted with linear or branched C₁-C₅ alkyl, linearor branched C₁-C₅ haloalkyl, and halogen. Examples of allylic ligandssuitable in the cationic complexes of the invention include but are notlimited to allyl, 2-chloroallyl, crotyl, 1,1-dimethyl allyl,2-methylallyl, 1-phenylallyl, 2-phenylallyl, and β-pinenyl.

Representative cationic complexes containing an allylic ligand are shownbelow.

In Structures VI, VIa, and VIb M, L′, L″, x and y are as previouslydefined.

Additional examples of allyl ligands are found in R. G. Guy and B. L.Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4,Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M. L. H.Green, R. B. King, R. Koster, P. L. I. Nagy, G. N. Schrauzer, Advancesin Organometallic Chemistry, Vol. 2, Academic Press Inc., New York,1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc., (1964)1585; and H. C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225; whichare all hereby incorporated by reference.

Representative neutral electron donor ligands under L′ include amines,pyridines organophosphorus containing compounds and arsines andstibines, of the formula:

E(R^(7′))₃

wherein E is arsenic or antimony, and R^(7′) is independently selectedfrom hydrogen, linear or branched C₁-C₁₀ alkyl, C₅-C₁₀ cycloalkyl,linear or branched C₁-C₁₀ alkoxy, allyl, linear or branched C₂-C₁₀alkenyl, C₆-C₁₂ aryl, C₆-C₁₂ aryloxy, C₆-C₁₂ arylsufides (e.g., PhS),C₇-C₁₈ aralkyl, cyclic ethers and thioethers, tri(linear or branchedC₁-C₁₀ alkyl)silyl, tri(C₆-C₁₂ aryl)silyl, tri(linear or branched C₁-C₁₀alkoxy)silyl, triaryloxysilyl, tri(linear or branched C₁-C₁₀alkyl)siloxy, and tri(C₆-C₁₂ aryl)siloxy, each of the foregoingsubstituents can be optionally substituted with linear or branched C₁-C₅alkyl, linear or branched C₁-C₅ haloalkyl, C₁-C₅ alkoxy, halogen, andcombinations thereof. Representative alkyl groups include but are notlimited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,decyl, and dodecyl. Representative cycloalkyl groups include but are notlimited to cyclopentyl and cyclohexyl. Representative alkoxy groupsinclude but are not limited to methoxy, ethoxy, and isopropoxy.Representative cyclic ether and cyclic thioether groups include but arenot limited furyl and thienyl, respectively. Representative aryl groupsinclude but are not limited to phenyl, o-tolyl, and naphthyl.Representative aralkyl groups include but are not limited to benzyl, andphenylethyl (i.e., —CH₂CH₂PH). Representative silyl groups include butare not limited to triphenylsilyl, trimethylsilyl, and triethylsilyl. Asin the general definition above each of the foregoing groups can beoptionally substituted with linear or branched C₁-C₅ alkyl, linear orbranched C₁-C₅ haloalkyl, and halogen.

Representative pyridines include lutidine (including 2,3-; 2,4-; 2,5-;2,6-; 3,4-; and 3,5-substituted), picoline (including 2-,3-, or4-substituted), 2,6-di-t-butylpyridine, and 2,4-di-t-butylpyridine.

Representative arsines include triphenylarsine, triethylarsine, andtriethoxysilylarsine.

Representative stibines include triphenylstibine andtrithiophenylstibine.

Suitable amine ligands can be selected from amines of the formulaN(R^(8′))₃, wherein R^(8′) independently represents hydrogen, linear orbranched C₁-C₂₀ alkyl, linear or branched C₁-C₂₀ haloalkyl, substitutedand unsubstituted C₃-C₂₀ cycloalkyl, substituted and unsubstitutedC₆-C₁₈ aryl, and substituted and unsubstituted C₇-C₁₈ aralkyl. Whensubstituted, the cycloalkyl, aryl and aralkyl groups can bemonosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear or branched C₁-C₂ alkyl,linear or branched C₁-C₅ haloalkyl, linear or branched C₁-C₅ alkoxy,C₆-C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.Representative amines include but are not limited to ethylamine,triethylamine, diisopropylamine, tributylamine, N,N-dimethylaniline,N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-4-t-octylaniline, andN,N-dimethyl-4-hexadecylaniline.

The organophosphorus containing ligands include phosphines, phosphites,phosphonites, phosphinites and phosphorus containing compounds of theformula:

P(R^(7′))_(g)[X′(R^(7′))_(h)]_(3−g)

wherein X′ is oxygen, nitrogen, or silicon, R^(7′) is as defined aboveand each R^(7′) substituent is independent of the other, g is 0, 1, 2,or 3, and h is 1, 2, or 3, with the proviso that when X′ is a siliconatom, h is 3, when X′ is an oxygen atom h is 1, and when X′ is anitrogen atom, h is 2. When g is 0 and X′ is oxygen, any two or 3 ofR^(7′) can be taken together with the oxygen atoms to which they areattached to form a cyclic moiety. When g is 3 any two of R⁷ can be takentogether with the phosphorus atom to which they are attached torepresent a phosphacycle of the formula:

wherein R^(7′) is as previously defined and h′ is an integer from 4 to11.

The organophosphorus compounds can also include bidentate phosphineligands of the formulae:

wherein R⁷ is as previously defined and i is 0, 1, 2, or 3 are alsocontemplated herein.

Representative phosphine ligands include, but are not limited totrimethylphosphine, triethylphosphine, tri-n-propylphosphine,triisopropylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine,tri-i-butylphosphine, tri-t-butylphosphine, tricyclopentylphosphine,triallylphosphine, tricyclohexylphosphine, triphenylphosphine,trinaphthylphosphine, tri-p-tolylphosphine, tri-o-tolylphosphine,tri-m-tolylphosphine, tribenzylphosphine,tri(p-trifluoromethylphenyl)phosphine, tris(trifluoromethyl)phosphine,tri(p-fluorophenyl)phosphine, tri(p-trifluoromethylphenyl)phosphine,allyldiphenylphosphine, benzyldiphenylphosphine, bis(2-furyl)phosphine,bis(4-methoxyphenyl)phenylphosphine, bis(4-methylphenyl)phosphine,bis(3,5-bis(trifluoromethyl)phenyl)phosphine,t-butylbis(trimethylsilyl)phosphine, t-butyldiphenylphosphine,cyclohexyldiphenylphosphine, diallylphenylphosphine, dibenzylphosphine,dibutylphenylphosphine, dibutylphosphine, di-t-butylphosphine,dicyclohexylphosphine, diethylphenylphosphine, di-i-butylphosphine,dimethylphenylphosphine, dimethyl(trimethylsilyl)phosphine,diphenylphosphine, diphenylpropylphosphine, diphenyl(p-tolyl)phosphine,diphenyl(trimethylsilyl)phosphine, diphenylvinylphosphine,divinylphenylphosphine, ethyldiphenylphosphine,(2-methoxyphenyl)methylphenylphosphine, tri-n-octylphosphine,tris(3,5-bis(trifluoromethyl)phenyl)phosphine,tris(3-chlorophenyl)phosphine, tris(4-chlorophenyl)phosphine,tris(2,6-dimethoxyphenyl)phosphine, tris(3-fluorophenyl)phosphine,tris(2-furyl)phosphine, tris(2-methoxyphenyl)phosphine,tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine,tris(3-methoxypropyl)phosphine, tris(2-thienyl)phosphine,tris(2,4,6-trimethylphenyl)phosphine, tris(trimethylsilyl)phosphine,isopropyldiphenylphosphine, dicyclohexylphenylphosphine,(+)-neomenthyldiphenylphosphine, tribenzylphosphine,diphenyl(2-methoxyphenyl)phosphine,diphenyl(pentafluorophenyl)phosphine,bis(pentafluorophenyl)phenylphosphine, andtris(pentafluorophenyl)phosphine.

Exemplary bidentate phosphine ligands include but are not limited to(R)-(+)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl;bis(dicyclohexylphosphino)methane; bis(dicyclohexylphosphino)ethane;bis(diphenylphosphino)methane; bis(diphenylphosphino)ethane.

The phosphine ligands can also be selected from phosphine compounds thatare water soluble thereby imparting the resulting catalysts withsolubility in aqueous media. Selected phosphines of this type includebut are not limited to carboxylic substituted phosphines such as4-(diphenylphosphine)benzoic acid, and 2-(diphenylphosphine)benzoicacid, sodium 2-(dicyclohexylphosphino)ethanesulfonate,4,4′-(phenylphosphinidene)bis(benzene sulfonic acid) dipotassium salt,3,3′,3″-phosphinidynetris(benzene sulfonic acid) trisodium salt,4-(dicyclohexylphosphino)-1,1-dimethylpiperidinium chloride,4-(dicyclohexylphosphino)-1,1-dimethylpiperidinium iodide, quaternaryamine-functionalized salts of phosphines such as2-(dicyclohexylphosphino)-N,N,N-trimethylethanaminium chloride,2,2′-(cyclohexylphosphinidene)bis[N,N,N-trimethylethanaminiumdichloride,2,2′-(cyclohexylphosphinidene)bis(N,N,N-trimethylethanaminium)diiodide,and 2-(dicyclohexylphosphino)-N,N,N-trimethylethanaminium iodide.

Examples of phosphite ligands include but are not limited totrimethylphosphite, diethylphenylphosphite, triethylphosphite,tris(2,4-di-t-butylphenyl)phosphite, tri-n-propylphosphite,triisopropylphosphite, tri-n-butylphosphite, tri-sec-butylphosphite,triisobutylphosphite, tri-t-butylphosphite, dicyclohexylphosphite,tricyclohexylphosphite, triphenylphosphite, tri-p-tolylphosphite,tris(p-trifluoromethylphenyl)phosphite, benzyldiethylphosphite, andtribenzylphosphite.

Examples of phosphinite ligands include but are not limited to methyldiphenylphosphinite, ethyl diphenylphosphinite, isopropyldiphenylphosphinite, and phenyl diphenylphosphinite.

Examples of phosphonite ligands include but are not limited to diphenylphenylphosphonite, dimethyl phenylphosphonite, diethylmethylphosphonite, diisopropyl phenylphosphonite, and diethylphenylphosphonite.

Representative labile neutral electron donor ligands (L″) are reactiondiluent, reaction monomers, DMF, DMSO, dienes including C₄ to C₁₀aliphatic and C₄ to C₁₀ cycloaliphatic dienes representative dienesinclude butadiene, 1,6-hexadiene, and cyclooctadiene (COD), water,chlorinated alkanes, alcohols, ethers, ketones, nitriles, arenes,phosphine oxides, organic carbonates and esters.

Representative chlorinated alkanes include but are not limited todichloromethane, 1,2-dichloroethane, and carbon tetrachloride.

Suitable alcohol ligands can be selected from alcohols of the formulaR^(9′)OH, wherein R^(9′) represents linear or branched C₁-C₂₀ alkyl,linear or branched C₁-C₂₀ haloalkyl, substituted and unsubstitutedC₃-C₂₀ cycloalkyl, substituted and unsubstituted C₆-C₁₈ aryl, andsubstituted and unsubstituted C₆-C₁₈ aralkyl. When substituted, thecycloalkyl, aryl and aralkyl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom hydrogen, linear or branched C₁-l₂ alkyl, linear or branched C₁-C₅haloalkyl, linear or branched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogenselected from chlorine, bromine, and fluorine. Representative alcoholsinclude but are not limited to methanol, ethanol, n-propanol,isopropanol, butanol, hexanol, t-butanol, neopentanol, phenol,2,6-di-i-propylphenol, 4-t-octylphenol, 5-norbornene-2-methanol, anddodecanol.

Suitable ether ligands and thioether ligands can be selected from ethersand thioethers of the formulae (R^(10′)—O—R^(10′)) and(R^(10′)—S—R^(10′)), respectively, wherein R^(10′) independentlyrepresents linear or branched C₁-C₁₀ alkyl radicals, linear or branchedC₁-C₂₀ haloalkyl, substituted and unsubstituted C₃-C₂₀ cycloalkyl,linear or branched C₁-C₂₀ alkoxy substituted and unsubstituted C₆-C₁₈aryl, and substituted and unsubstituted C₆-C₁₈ aralkyl. Whensubstituted, the cycloalkyl, aryl and aralkyl groups can bemonosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear or branched C₁-C₁₂ alkyl,linear or branched C₁-C₅ haloalkyl, linear or branched C₁-C₅ alkoxy,C₆-C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.taken together along with the oxygen or sulfur atom to which they areattached to form a cyclic ether or cyclic thioether. Representativeethers include but are not limited to dimethyl ether, dibutyl ether,methyl-t-butyl ether, di-i-propyl ether, diethyl ether, dioctyl ether,1,4-dimethoxyethane, THF, 1,4-dioxane and tetrahydrothiophene. Suitableketone ligands are represented by ketones of the formulaR^(11′)C(O)R^(11′) wherein R^(11′) independently represents hydrogen,linear or branched C₁-C₂₀ alkyl, linear or branched C₁-C₂₀ haloalkyl,substituted and unsubstituted C₃-C₂₀ cycloalkyl, substituted andunsubstituted C₆-C₁₈ aryl, and substituted and unsubstituted C₆-C₁₈aralkyl. When substituted, the cycloalkyl, aryl and aralkyl groups canbe monosubstituted or multisubstituted, wherein the substituents areindependently selected from hydrogen, linear or branched C₁-C₁₂ alkyl,linear or branched C₁-C₅ haloalkyl, linear or branched C₁-C, alkoxy,C₆-C₁₂ aryl, and halogen selected from chlorine, bromine, and fluorine.Representative ketones include but are not limited to acetone, methylethyl ketone, cyclohexanone, and benzophenone.

The nitrile ligands can be represented by the formula R^(12′)CN, whereinR^(12′) represents hydrogen, linear or branched C₁-C₂₀ alkyl, linear orbranched C₁-C₂₀ haloalkyl, substituted and unsubstituted C₃-C₂₀cycloalkyl, substituted and unsubstituted C₆-C₁₈ aryl, and substitutedand unsubstituted C₆-C₁₈ aralkyl. When substituted, the cycloalkyl, aryland aralkyl groups can be monosubstituted or multisubstituted, whereinthe substituents are independently selected from hydrogen, linear orbranched C₁-C₁₂ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogen selected from chlorine,bromine, and fluorine. Representative nitriles include but are notlimited to acetonitrile, propionitrile, benzonitrile, benzyl cyanide,and 5-norbornene-2-carbonitrile.

The arene ligands can be selected from substituted and unsubstitutedC₆-C₁₂ arenes containing monosubstitution or multisubstitution, whereinthe substituents are independently selected from hydrogen, linear orbranched C₁-C₁₂ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogen selected from chlorine,bromine, and fluorine. Representative arenes include but are not limitedto toluene, benzene, o-, m-, and p-xylenes, mesitylene, fluorobenzene,o-difluorobenzene, p-difluorobenzene, chlorobenzene, pentafluorobenzene,o-dichlorobenzene, and hexafluorobenzene.

Suitable trialkyl and triaryl phosphine oxide ligands can be representedby phosphine oxides of the formula P(O)(R^(13 ′)) ₃, wherein R^(13′)independently represents linear or branched C₁-C₂₀ alkyl, linear orbranched C₁-C₂₀ haloalkyl, substituted and unsubstituted C₃-C₂₀cycloalkyl, linear or branched C₁-C₂₀ alkoxy, linear or branched C₁-C₂₀haloalkoxy, substituted and unsubstituted C₆-C₁₈ aryl, and substitutedand unsubstituted C₆-C₁₈ aralkyl. When substituted, the cycloalkyl, aryland aralkyl groups can be monosubstituted or multisubstituted, whereinthe substituents are independently selected from hydrogen, linear orbranched C₁-C₂ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, C₆-C₁₂ aryl, and halogen selected from chlorine,bromine, and fluorine. Representative phosphine oxides include but arenot limited to triphenylphosphine oxide, tributylphosphine oxide,trioctylphosphine oxide, tributylphosphate, andtris(2-ethylhexyl)phosphate.

Representative carbonates include but are not limited to ethylenecarbonate and propylene carbonate.

Representative esters include but are not limited to ethyl acetate andi-amyl acetate.

WCA Description

The weakly coordinating counteranion complex, [WCA], of Formula I can beselected from borates and aluminates, boratobenzene anions, carboraneand halocarborane anions.

The borate and aluminate weakly coordinating counteranions arerepresented by Formulae II and III below:

[M′(R^(24′))(R^(25′))(R^(26′))(R^(27′))]⁻

[M′(OR^(28′))(OR^(29′))(OR^(30′))(OR^(31′))]⁻

wherein in Formula II M′ is boron or aluminum and R^(24′), R^(25′),R^(26′), and R^(27′) independently represent fluorine, linear orbranched C₁-C₁₀ alkyl, linear or branched C₁-C₁₀ alkoxy, linear orbranched C₃-C₅ haloalkenyl, linear or branched C₃-C₁₂ trialkylsiloxy,C₁₈-C₃₆ triarylsiloxy, substituted and unsubstituted C₆-C₃₀ aryl, andsubstituted and unsubstituted C₆-C₃₀ aryloxy groups wherein R^(24′) toR^(27′) can not all simultaneously represent alkoxy or aryloxy groups.When substituted the aryl groups can be monosubstituted ormultisubstituted, wherein the substituents are independently selectedfrom linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,linear or branched C₁-C₅ alkoxy, linear or branched C₁-C₅ haloalkoxy,linear or branched C₁-C₁₂ trialkylsilyl, C₆-C₁₈ triarylsilyl, andhalogen selected from chlorine, bromine, and fluorine. In anotherembodiment, the halogen is fluorine.

Representative borate anions under Formula II include but are notlimited to tetrakis(pentafluorophenyl)borate,tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate,tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5,6-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,methyltris(perfluorophenyl)borate, ethyltris(perfluorophenyl)borate,phenyltris(perfluorophenyl)borate,tetrakis(1,2,2-trifluoroethylenyl)borate,tetrakis(4-tri-i-propylsilyltetrafluorophenyl)borate,tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate,(triphenylsiloxy)tris(pentafluorophenyl)borate,(octyloxy)tris(pentafluorophenyl)borate,tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,andtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate.

Representative aluminate anions under Formula II include but are notlimited to tetrakis(pentafluorophenyl)aluminate,tris(perfluorobiphenyl)fluoroaluminate,(octyloxy)tris(pentafluorophenyl)aluminate,tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, andmethyltris(pentafluorophenyl)aluminate.

In Formula III M′ is boron or aluminum, R^(28′), R^(29′), R^(30′), andR^(31′) independently represent linear or branched C₁-C₁₀ alkyl, linearor branched C₁-C₁₀ haloalkyl, C₂-C₁₀ haloalkenyl, substituted andunsubstituted C₆-C₃₀ aryl, and substituted and unsubstituted C₇-C₃₀aralkyl groups, subject to the proviso that at least three of R^(28′) toR^(31′) must contain a halogen containing substituent. When substitutedthe aryl and aralkyl groups can be monosubstituted or multisubstituted,wherein the substituents are independently selected from linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, linear or branched C₁-C₁₀ haloalkoxy, and halogenselected from chlorine, bromine, and fluorine. In another embodiment,the halogen is fluorine. The groups OR^(28′) and OR^(29′) can be takentogether to form a chelating substituent represented by —O—R^(32′)—O—,wherein the oxygen atoms are bonded to M′ and R^(32′) is a divalentradical selected from substituted and unsubstituted C₆-C₃₀ aryl andsubstituted and unsubstituted C₇-C₃₀ aralkyl. In one embodiment, theoxygen atoms are bonded, either directly or through an alkyl group, tothe aromatic ring in the ortho or meta position. When substituted thearyl and aralkyl groups can be monosubstituted or multisubstituted,wherein the substituents are independently selected from linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, linear orbranched C₁-C₅ alkoxy, linear or branched C₁-C₁₀ haloalkoxy, and halogenselected from chlorine, bromine, and fluorine. In another embodiment,the halogen is fluorine. Representative structures of divalent R^(32′)radicals are illustrated below:

wherein R^(33′) independently represents hydrogen, linear or branchedC₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, and halogen selectedfrom chlorine, bromine, and fluorine (in another embodiment, the halogenis fluorine); R^(34′) can be a monosubstituent or taken up to four timesabout each aromatic ring depending on the available valence on each ringcarbon atom and independently represents hydrogen, linear or branchedC₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, linear or branchedC₁-C₅ alkoxy, linear or branched C₁-C₁₀ haloalkoxy, and halogen selectedfrom chlorine, bromine, and fluorine (in one embodiment, the halogen isfluorine); and n″ independently represents an integer from 0 to 6. Itshould be recognized that when n″ is 0 the oxygen atom in the formula—O—R^(32′)—O— is bonded directly to a carbon atom in the aromatic ringrepresented by R^(32′). In the above divalent structural formulae theoxygen atom(s), i.e., when n″ is 0, and the methylene or substitutedmethylene group(s), —(C(R^(33′))₂)_(n″)—, are, in one embodiment,located on the aromatic ring in the ortho or meta positions.Representative chelating groups of the formula —O—R^(32′)—O— include butare not limited to are 2,3,4,5-tetrafluorobenzenediolate (—OC₆F₄O—),2,3,4,5-tetrachlorobenzenediolate (—OC₆Cl₄O—), and2,3,4,5-tetrabromobenzenediolate (—OC₆Br₄O—), andbis(1,1′-bitetrafluorophenyl-2,2′-diolate).

Representative borate and aluminate anions under Formula III include butare not limited to [B(OC(CF₃)₃)₄]⁻, [B(OC(CF₃)₂(CH₃))₄]⁻,[B(OC(CF₃)₂H)₄]⁻, [B(OC(CF₃)(CH₃)H)₄]⁻, [Al(OC(CF₃)₂Ph)₄]⁻,[B(OCH₂(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₄CH₃)₄]⁻, [Al(OC(CF₃)₃)₄]⁻,[Al(OC(CF₃)(CH₃)H)₄]⁻, [Al(OC(CF₃)₂H)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-i-Pr)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-t-butyl)₄]⁻,[Al(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,]⁻, [Al(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,]⁻,[Al(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄]⁻,[Al(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄]⁻, [Al(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄]⁻, and[Al(OC(CF₃)₂C₆F₅)₄]⁻.

The boratobenzene anions useful as the weakly coordinating counteranioncan be represented by Formula IV below:

wherein R^(34′) is selected from fluorine, fluorinated hydrocarbyl,perfluorocarbyl, and fluorinated and perfluorinated ethers. As used hereand throughout the specification, the term halohydrocarbyl means that atleast one hydrogen atom on the hydrocarbyl radical, e.g., alkyl,alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups, is replaced witha halogen atom selected from chlorine, bromine, iodine, and fluorine(e.g., haloalkyl, haloalkenyl, haloalkynyl, halocycloalkyl, haloaryl,and haloaralkyl). The term fluorohydrocarbyl means that at least onehydrogen atom on the hydrocarbyl radical is replaced by fluorine. Thedegree of halogenation can range from at least one hydrogen atom beingreplaced by a halogen atom (e.g., a monofluoromethyl group) to fullhalogenation (perhalogenation) wherein all hydrogen atoms on thehydrocarbyl group have been replaced by a halogen atom (e.g.,perhalocarbyl such as trifluoromethyl (perfluoromethyl)). Thefluorinated hydrocarbyl and perfluorocarbyl radicals contain, in oneembodiment, 1 to 24 carbon atoms. In another embodiment, the fluorinatedhydrocarbyl and perfluorocarbyl radicals contain 1 to 12 carbon atoms.In yet another embodiment, fluorinated hydrocarbyl and perfluorocarbylradicals contain 6 carbon atoms and can be linear or branched, cyclic,or aromatic. The fluorinated hydrocarbyl and perfluorocarbyl radicalsinclude but are not limited to fluorinated and perfluorinated linear orbranched C₁-C₂₄ alkyl, fluorinated and perfluorinated C₃-C₂₄ cycloalkyl,fluorinated and perfluorinated C₂-C₂₄ alkenyl, fluorinated andperfluorinated C₃-C₂₄ cycloalkenyl, fluorinated and perfluorinatedC₆-C₂₄ aryl, and fluorinated and perfluorinated C₇-C₂₄ aralkyl. Thefluorinated and perfluorocarbyl ether substituents are represented bythe formulae —(CH₂)_(m)OR^(36′), or —(CF₂)_(m)OR^(36′) respectively,wherein R^(36′) is a fluorinated or perfluorocarbyl group as definedabove, m is and integer of 0 to 5. It is to be noted that when m is 0the oxygen atom in the ether moiety is directly bonded attached to theboron atom in the boratobenzene ring.

In one embodiment, R^(34′) radicals include those that are electronwithdrawing in nature such as, for example, fluorinated andperfluorinated hydrocarbyl radicals selected from trifluoromethyl,perfluoroethyl, perfluoropropyl, perfluoroisopropyl, pentafluorophenyland bis(3,5-trifluoromethyl)phenyl.

R^(35′) independently represents hydrogen, halogen, perfluorocarbyl, andsilylperfluorocarbyl radicals, wherein the perfluorocarbyl andsilylperfluorocarbyl are as defined previously. In one embodiment, thehalogen groups are selected from chlorine, fluorine. In anotherembodiment, the halogen is fluorine. When R^(35′) is halogen,perfluorocarbyl, and/or silylperfluorocarbyl, the radical(s) are, in oneembodiment, ortho or para to the boron atom in the boratobenzene ring.In another embodiment, when R^(35′) is halogen, perfluorocarbyl, and/orsilylperfluorocarbyl, the radical(s) are para to the boron atom in theboratobenzene ring.

Representative boratobenzene anions include but are not limited to[1,4-dihydro4-methyl-1-(pentafluorophenyl)]-2-borate,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borate,1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borate, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borate.

The carborane and halocarborane anions useful as the weakly coordinatingcounteranion include but are not limited to CB₁₁(CH₃)₁₂ ⁻, CB₁₁H₁₂ ⁻,1-C₂H₅CB₁₁H₁₁ ⁻, 1-Ph₃SiCB₁₁H₁₁ ⁻, 1-CF₃CB₁₁H₁₁ ⁻, 12-BrCB₁₁ H₁₁ ⁻,12-BrCB₁₁H₁₁ ⁻, 7,12-Br₂CB₁₁H₁₀ ⁻, 12-ClCB₁₁H₁₁ ⁻, 7,12-Cl₂CB₁₁H₁₀ ⁻;1-H—CB₁₁F₁₁ ⁻, 1-CH₃—CB₁₁F₁₁ ⁻, 1-CF₃—CB₁₁F₁₁ ⁻, 12-CB₁₁H₁₁F⁻,7,12-CB₁₁H₁₁F₂ ⁻, 7,9,12-CB₁₁H₁₁F₃ ⁻, CB₁₁H₆Br₆ ⁻; 6-CB₉H₉F⁻,6,8-CB₉H₈F₂ ⁻, 6,7,8-CB₉H₇F₃ ⁻, 6,7,8,9-CB₉H₆F₄ ⁻, 2,6,7,8,9-CB₉H₅F₅ ⁻,CB₉H₅Br₅ ⁻, CB₁₁H₆Cl₆ ⁻, CB₁₁H₆F₆ ⁻, CB₁₁H₆F₆ ⁻, CB₁₁H₆I₆ ⁻, CB₁₁H₆Br₆⁻, 6,7,9,10,11,12-CB₁₁H₆F₆ ⁻, 2,6,7,8,9,10-CB₉H₅F₅ ⁻, 1-H—CB₉F₉ ⁻,12-CB₁₁H₁₁(C₆H₅)⁻, 1-C₆F₅—CB₁₁H₅Br₆ ⁻, CB₁₁Me₁₂ ⁻, CB₁₁(CF₃)₁₂ ⁻,Co(B₉C₂H₁₁)₂ ⁻, CB₁₁(CH₃)₁₂ ⁻, CB₁₁(C₄H₉)₁₂ ⁻, CB₁₁(C₆H₁₃)₁₂ ⁻,Co(C₂B₉H₁₁)₂ ⁻, Co(Br₃C₂B₉H₈)₂ ⁻ and dodecahydro-1-carbadodecaborate.

Catalyst Preparation

The catalysts of Formula I can be prepared as a preformed singlecomponent catalyst in solvent or can be prepared in situ by admixing thecatalyst precursor components in the desired monomer to be polymerized.

The single component catalyst of Formula I can be prepared by admixingthe catalyst precursors in an appropriate solvent, allowing the reactionto proceed under appropriate temperature conditions, and isolating thecatalyst product. In another embodiment, a Group 10 metal pro-catalystis admixed with a Group 15 electron donor compound and/or a labileneutral electron donor compound, and a salt of a weakly coordinatinganion in an appropriate solvent to yield the preformed catalyst complexset forth under Formula I above. In another embodiment a Group 10 metalpro-catalyst containing a Group 15 electron donor ligand is admixed witha salt of a weakly coordinating anion in an appropriate solvent to yieldthe preformed catalyst complex.

The catalyst preparation reactions are carried out in solvents that areinert under the reaction conditions. Examples of solvents suitable forthe catalyst preparation reaction include but are not limited to alkaneand cycloalkane solvents such as pentane, hexane, heptane, andcyclohexane; halogenated alkane solvents such as dichloromethane,chloroform, carbon tetrachloride, ethylchloride, 1,1-dichloroethane,1,2-dichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane,2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane; etherssuch as THF and diethylether; aromatic solvents such as benzene, xylene,toluene, mesitylene, chlorobenzene, and o-dichlorobenzene; andhalocarbon solvents such as Freon® 112; and mixtures thereof. In oneembodiment, solvents include, for example, benzene, fluorobenzene,o-difluorobenzene, p-difluorobenzene, pentafluorobenzene,hexafluorobenzene, o-dichlorobenzene, chlorobenzene, toluene, o-, m-,and p-xylenes, mesitylene, cyclohexane, THF, and dichloromethane.

A suitable temperature range for carrying out the reaction is from about−80° C. to about 150° C. In another embodiment, the temperature rangefor carrying out the reaction is from about −30° C. to about 100° C. Inyet another embodiment, the temperature range for carrying out thereaction is from about 0° C. to about 65° C. In still yet anotherembodiment, the temperature range for carrying out the reaction is fromabout 10° C. to about 40° C. Pressure is not critical but may depend onthe boiling point of the solvent employed, i.e. sufficient pressure tomaintain the solvent in the liquid phase. Reaction times are notcritical, and can range from several minutes to 48 hours. In oneembodiment, the reactions are carried out under inert atmosphere such asnitrogen or argon.

The reaction is carried out by dissolving the pro-catalyst in a suitablesolvent and admixing the appropriate ligand(s) and the salt of thedesired weakly coordinating anion with the dissolved pro-catalyst, andoptionally heating the solution until the reaction is complete. Thepreformed single component catalyst can be isolated or can be useddirectly by adding aliquots of the preformed catalyst in solution to thepolymerization medium. Isolation of the product can be accomplished bystandard procedures, such as evaporating the solvent, washing the solidwith an appropriate solvent, and then recrystallizing the desiredproduct. The molar ratios of catalyst components employed in thepreparation the preformed single component catalyst of the invention isbased on the metal contained in the pro-catalyst component. In oneembodiment, the molar ratio of pro-catalyst/Group 15 electron donorcomponent/WCA salt is 1:1-10:1-100, In another embodiment, the molarratio of pro-catalyst/Group 15 electron donor component/WCA salt is1:1-5:1-20. In yet another embodiment, the molar ratio ofpro-catalyst/Group 15 electron donor component/WCA salt is 1:1-2:1-5. Inembodiments of the invention where the pro-catalyst is ligated with aGroup 15 electron donor ligand and/or a labile neutral electron donorligand the molar ratio of pro-catalyst (based on the metal content) toWCA salt is 1:1-100. In another embodiment, this ratio is 1:1-20. In yetanother embodiment, this ratio is 1:1-5.

In one embodiment, a Group 10 metal pro-catalyst dimer of the formula[R′MA′]₂ is admixed with a Group 15 electron donor compound, (L′), and asalt of a suitable weakly coordinating anion in an appropriate solventto produce the single component catalyst product as shown in equation(1) below.

[R′MA′]₂+xL′+yL″+[WCA]salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  1.

Suitable pro-catalyst dimers of the formula [R′MA′]₂ include but are notlimited to the following compositions (allyl)palladiumtrifluoroacetatedimer, (allyl)palladiumchloride dimer, (crotyl)palladiumchloride dimer,(allyl)palladiumiodide dimer, (β-pinenyl)palladiumchloride dimer,methallylpalladium chloride dimer, 1,1-dimethylallylpalladium chloridedimer, and (allyl)palladiumacetate dimer.

In another embodiment, a ligated Group 10 metal pro-catalyst of theformula [R′M(L″)_(y)A′] is admixed with a Group 15 electron donorcompound, (L′), and a salt of a suitable weakly coordinating anion in anappropriate solvent to produce the single component catalyst product asshown in equation (2) below.

 [R′M′(L″)_(y)A′]+xL′+[WCA]salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  2.

A representative pro-catalyst of the formula [R′M(L″)_(y)A′] includesbut is not limited to (COD)palladium (methyl)chloride.

In a further embodiment, a Group 10 metal ligated pro-catalyst of theformula [R′M(L′)_(x)A′] containing the Group 15 electron donor ligand(L′) is admixed with a salt of a suitable weakly coordinating anion inan appropriate solvent to produce the single component catalyst productas shown in equation (3) below.

[R′M′(L′)_(x)A′]+xL″+[WCA]salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  3.

Suitable pro-catalysts of the formula [R′M(L′)_(x)A′] include but arenot limited to the following compositions:

(allyl)palladium(tricyclohexylphosphine)chloride,(allyl)palladium(tricyclohexylphosphine)triflate,(allyl)palladium(triisopropylphosphine)triflate,(allyl)palladium(tricyclopentylphosphine)triflate,(allyl)palladium(tricyclohexylphosphine)trifluoroacetate (also referredto herein as Allyl Pd-PCy₃TFA),(allyl)palladium(tri-o-tolylphosphine)chloride,(allyl)palladium(tri-o-tolylphosphine)triflate,(allyl)palladium(tri-o-tolylphosphine)nitrate,(allyl)palladium(tri-o-tolylphosphine)acetate,(allyl)palladium(triisopropylphosphine)triflimide,(allyl)palladium(tricyclohexylphosphine)triflimide,(allyl)palladium(triphenylphosphine)triflimide,(allyl)palladium(trinaphthylphosphine)triflate,(allyl)palladium(tricyclohexylphosphine) p-tolylsulfonate,(allyl)palladium(triphenylphosphine)triflate,(allyl)palladium(triisopropylphosphine)trifluoroacetate,(allyl)platinum(tricyclohexylphosphine)chloride,(allyl)platinum(tricyclohexylphosphine)trifate,(1,1-dimethylallyl)palladium(triisopropylphosphine)trifluoroacetate.(2-chloroallyl)palladium(triisopropylphosphine)trifluoroacetate,(crotyl) palladium(triisopropylphosphine)triflate,(crotyl)palladium(tricyclohexylphosphine)triflate,(crotyl)palladium(tricyclopentylphosphine)triflate,(methallyl)palladium(tricyclohexylphosphine)triflate,(methallyl)palladium(triisopropylphosphine)triflate,(methallyl)palladium(tricyclopentylphosphine)triflate,(methallyl)palladium(tricyclohexylphosphine)chloride,(methallyl)palladium(triisopropylphosphine)chloride,(methallyl)palladium(tricyclopentylphosphine)chloride,(methallyl)palladium(tricyclohexylphosphine)triflimide.(methallyl)palladium(triisopropylphosphine)triflimide,(methallyl)palladium(tricyclopentylphosphine)triflimide,(methallyl)palladium(tricyclohexylphosphine)trifluoroacetate,(methallyl)palladium(triisopropylphosphine)trifluoroacetate,(methallyl)palladium(tricyclopentylphosphine)trifluoroacetate,(methallyl)palladium(tricyclohexylphosphine) acetate ,(methallyl)palladium(triisopropylphosphine)acetate,(methallyl)palladium(tricylopentylphosphine)acetate,(methallyl)nickel(tricyclohexylphosphine)triflate,{2-[(dimethylamino)methyl]phenyl-C,N-}palladium(tricyclohexylphosphine)chloride,[(dimethylamino)methyl]phenyl-C,N-}-palladium(tricyclohexyl-phosphine)triflate,(hydrido)palladium bis(tricyclohexylphosphine)triflate,(hydrido)palladium bis(tricyclohexylphosphine)formate (hydrido)palladiumbis(tricyclohexylphosphine)chloride, (hydrido)palladiumbis(triisopropylphosphine)chloride, (hydrido)palladiumbis(tricyclohexylphosphine)nitrate, (hydrido)palladiumbis(tricyclohexylphosphine)trifluoroacetate, and(hydrido)palladiumbis(triisopropylphosphine)triflate.

Other pro-catalyst components suitable for use in the foregoing processinclude (Me₂NCH₂C₆H₄)Pd(O₃SCF₃)P(cyclohexyl)₃ (i.e.,ortho-metallatedphenylmethlyenedimethylamino palladiumtricyclohexylphosphine), (allyl)Pd(P-i-Pr₃)C₆F₅, (allyl)Pd(PCy₃)C₆F₅,(CH₃)Pd(PMe₃)₂Cl, (C₂H₅ )Pd(PMe₃)₂Cl(Ph)Pd(PMe₃)₂Cl, (CH₃)Pd(PMe₃)₂Br,(CH₃)Pd(PMe₂Ph)₂Cl, (C₂H₅)Pd(PMe₃)₂Br, (C₂H₅)Pd(PMe₃)₂Br,(Ph)Pd(PMe₃)₂Br, (CH₃)Pd(PMe₃)NO₃, (CH₃)Pd(P(i-Pr)₃)₂O₃SCCF₃,(η¹-benzyl)Pd(PEt₃)₂Cl, (allyl)Pd(PMe₃)OC(O)CH₂CH═CH₂,(allyl)Pd(AsPh₃)Cl, (allyl)Pd(PPh₃)Cl, (allyl)Pd(SbPh₃)Cl,(methylallyl)Pd(PPh₃)Cl, (methylallyl)Pd(AsPh₃)Cl,(methylallyl)Pd(SbPh₃)Cl, (methylallyl)Pd(PBu₃)Cl, and(methylallyl)Pd(P[(OCH₂)₃]CH)Cl.

In another embodiment, the catalyst can be formed by protonating apro-catalyst of the formula:

in the presence of a Brønsted acid based WCA salt or an equivalentreaction utilizing a carbonium or silylium based WCA salt to yield anactive catalyst as illustrated in Eq. 4.

In this embodiment R′ is a divalent hydrocarbyl ligand of the formula—(C_(d)H_(2d))— that is taken together with the Group 10 metal center Mto form a metallacycle where d′ represents the number of carbon atoms inthe divalent hydrocarbyl backbone and is an integer from 3 to 10. Any ofthe hydrogen atoms on the divalent hydrocarbyl backbone can be replacedby linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,C₅-C₁₀. cycloalkyl, and C₆-C₁₀ aryl. The cycloalkyl and aryl moietiescan optionally be substituted with a halogen substituent selected frombromine, chlorine, fluorine, and iodine. In another embodiment, thehalogen is fluorine. In addition, any two or three of the alkylsubstituents taken together with the hydrocarbyl backbone carbon atomsto which they are attached can form an aliphatic or aromatic ringsystem. The rings can be monocyclic, polycyclic, or fused. Protonationoccurs at one of the hydrocarbyl/metal center bond interfaces to yield acation complex with a monovalent hydrocarbyl ligand coordinated to themetal center M.

In another embodiment a Group 10 metal ligated pro-catalyst of theformula [R′M(L′)_(x)(L″)_(y)A′] containing a Group 15 electron donorligand (L′) and a labile neutral electron donor ligand (L″) is admixedwith a salt of a suitable weakly coordinating anion in an appropriatesolvent to produce the single component catalyst product as shown inequation (5) below.

[R′M(L′)_(x)(L″)_(y)A′]+[WCA]salt→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  5.

Suitable pro-catalysts of the formula [R′M(L′)_(x)(L″)_(y)A′] includebut are not limited to the following compositions:

[(allyl)Pd(NCCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Cl₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Cl₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂-3,4,5,6-Br₄C₆)₂],[(allyl)Pd(HOCH₃)(P-i-Pr₃)][B(O₂C₆H₄)₂],[(allyl)Pd(OEt₂)(P-i-Pr₃)][BPh₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)],[SbF₆][(allyl)Pd(OEt₂)(P-i-Pr₃)][BF₄], [(allyl)Pd(OEt₂)(PCy₃)][BF₄],[(allyl)Pd(OEt₂)(PPh₃)][BF₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)][PF₆],[(allyl)Pd(OEt₂)(PCy₃)][PF₆], [(allyl)Pd(OEt₂)(PPh₃)][PF₆],[(allyl)Pd(OEt₂)(P-i-Pr₃)][ClO₄], [(allyl)Pd(OEt₂)(PCy₃)][ClO₄],[(allyl)Pd(OEt₂)(PPh₃)][ClO₄], [(allyl)Pd(OEt₂)(P-i-Pr₃)][SbF₆],[(allyl)Pd(OEt₂)(PCy₃)][SbF₆], and [(allyl)Pd(OEt₂)(PPh₃)][SbF₆].

In another embodiment of the invention the catalyst of Formula I isgenerated by reacting a pro-catalyst of the formula[M(L′)_(x)(L″)_(y)(A′)₂] with an organometallic compound of aluminum,lithium or magnesium, and a source of a weakly coordinating anion (WCA)or a strong Lewis Acid. In this embodiment the anionic hydrocarbylligand (R′) on the group 10 metal center (M) is supplied via reactionwith the organometallic compound to yield the active catalyst as shownbelow.

[M(L′)_(x)(L″)_(y)(A′)₂]+[WCA]salt or Strong Lewis Acid+organometaliccompound→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  6.

Examples of pro-catalysts suitable for use in this embodiment include:

nickel acetylacetonate, nickel carboxylates, nickel(II) chloride,nickel(II) bromide, nickel ethylhexanoate, nickel(II) trifluoroacetate,nickel(II) hexafluoroacetylacetonate, NiCl₂(PPh₃)₂, NiBr₂(P(p-tolyl)₃)₂,trans-PdCl₂(PPh₃)₂, palladium(II) bis(trifluoroacetate), palladium(II)acetylacetonate, (cyclooctadiene)palladium(II) dichloride,Pd(acetate)₂(PPh₃)₂, PdCl₂(PPh₃)₂ PdBr₂(PPh₃)₂ PdBr₂(P(p-tolyl)₃)₂,PdCI₂(P(o-tolyl)₃)₂, PdCI₂(P(cyclohexyl)₃)₂, palladium(II) bromide,palladium(II) chloride, palladium(II) iodide, palladium(II)ethylhexanoate, dichloro bis(acetonitrile)palladium(II), dibromobis(benzonitrile)palladium(II), platinum(II) chloride, platinum(II)bromide, and platinum bis(triphenylphosphine)dichoride.

In general the Group 10 metal pro-catalyst is a nickel(II), platinum(II)or palladium(II) compound containing two anionic leaving groups (A′),which can be readily displaced by the weakly coordinating anion that isprovided by the WCA salt or strong Lewis acid described below and can bereplaced by hydrocarbyl groups originating from the organometalliccompound. The leaving groups can be the same or different. The Group 10metal pro-catalyst may or may not be ligated.

When the pro-catalyst of this embodiment is not ligated with a Group 15electron donor component (L′), the Group 15 electron donor ligand can beadded to the reaction medium as shown in the following reaction scheme.

[M(L″)_(y)(A′)₂]+xL′+[WCA] salt or Strong Lewis Acid+organometalliccompound→[R′M(L′)_(x)(L″)_(y)]_(b)[WCA]_(d)  7.

The strong Lewis acids suitable for use in this embodiment are selectedfrom compounds of the formula:

 M′(R^(41′))₃

wherein M′ represents aluminum or boron and R^(41′) representsmonosubstituted and multisubstituted C₆-C₃₀ aryl, wherein thesubstituents on the aryl group are independently selected from halogen(in one embodiment, the halogen is fluorine), linear or branched C₁-C₅haloalkyl (in one embodiment, trifluoromethyl), and halogenated andperhalogenated phenyl (in one embodiment, pentafluorophenyl). Examplesof such strong Lewis acids include: tris(pentafluorophenyl)boron,tris(3,5-bis(trifluoromethyl)phenyl)boron,tris(2,2′,2″-nonafluorobiphenyl)borane, andtris(pentafluorophenyl)aluminum.

The organometallic compound is a hydrocarbyl derivative of silicon,germanium, tin, lithium, magnesium or aluminum. In one embodiment,aluminum derivatives are utilized. The organoaluminum component of thecatalyst system is represented by the formula:

AlR′_(3−x″)Q_(x″)

wherein R′ independently represents hydrogen, linear or branched C₁-C₂₀alkyl, C₅-C₁₀ cycloalkyl, linear or branched C₂-C₂₀ alkenyl, C₆-C₁₅cycloalkenyl, allylic ligands or canonical forms thereof, C₆-C₂₀ aryl,and C₇-C₃₀ aralkyl, Q is a halide or pseudohalide selected fromchlorine, fluorine, bromine, iodine, linear and unbranched C₁-C₂₀alkoxy, C₆-C₂₄ aryloxy; x″ is 0 to 2.5. In another embodiment, x″ is 0to 2. In yet another embodiment, x″ is 0 to 1. In one embodiment,trialkylaluminum compounds are used. Examples of suitable organometalliccompounds include: methyllithium, sec-butyllithium, n-butyllithium,phenyllithium, butylethylmagnesium, di-n-butylmagnesium,butyloctylmagnesium, trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-i-propylaluminum, tri-i-butylaluminum,tri-2-methylbutylaluminum, tri-octylaluminum, diethylaluminum chloride,ethylaluminum dichloride, di-i-butylaluminum chloride, diethylaluminumbromide, ethylaluminum sesquichloride, diethylaluminum ethoxide,diethylaluminum(i-butylphenoxide), anddiethylaluminum(2,4-di-tert-butylphenoxide).

Embodiments of the catalyst devoid of a hydrocarbyl containing ligandcan be synthesized by reacting a pro-catalyst of the formula [M(A′)₂]with the desired ligands and WCA salt in accordance with the followingreaction scheme:

[M(A′)₂]+xL′+2[WCA] salt→[M(L′)_(x)][WCA]₂+2A′ salt wherein x=1 or 2, M,and L′ are as previously defined.  8.

Examples of pro-catalyst compounds include palladium(II)bis(acetylacetonate, palladium (acetate)₂, Pd(NO₃)₂, PdCl₂, PdBr₂, andPdl₂.

The foregoing schematic equations (1 to 8) have been presented forillustrative purposes only. While they have been written in balancedform, it should be recognized that an excess of reaction components canbe employed without deviating from the spirit of invention. For example,an excess of L′, L″, A′, or WCA salt containing components can beemployed in the process of the invention so long as the process is notdeleteriously affected.

In a one embodiment the molar ratio of the Group 10 metal/Group 15electron donor compound/source of a weakly coordinatinganion/organometallic compound is 1:1-10:1-100:2-200. In anotherembodiment, the molar ratio of the Group 10 metal/Group 15 electrondonor compound/source of a weakly coordinating anion/organometalliccompound is 1:1-5:1-40:4-100. In yet another embodiment, the molar ratioof the Group 10 metal/Group 15 electron donor compound/source of aweakly coordinating anion/organometallic compound is 1:1-2:2-20:5-50. Inembodiments where the Group 10 metal ion source is an adduct containinga Group 15 electron donor compound, no additional Group 15 electrondonor compound need be employed. In this embodiment the molar ratio ofthe Group 10 metal/Group 15 electron donor compound/source of a weaklycoordinating anion/organometallic compound is 1:0:2-20:5-50.

In all of the forgoing embodiments the catalysts of Formula I can beprepared as a preformed single component catalyst in solvent or they canbe prepared in situ by admixing the precursor components (ligated ornon-ligated Group 10 metal component with leaving group(s), ligandcomponent(s), and WCA source or strong Lewis acid source) in the desiredmonomer, monomer mixtures, or solutions thereof. It is also possible toadmix two or even three of the catalyst precursor components and thenadd the mixture to the monomer or monomer solution containing theremaining catalyst precursor component(s).

In the equations and formulae set forth above and throughout thespecification, R′, M, L′, L″, [WCA], b, d, x, and y are as defined aboveunless otherwise defined, A′ is an anionic leaving group which isdefined below, [WCA] salt is a metal salt of the weakly coordinatinganion [WCA], and the abbreviations Me, Et, Pr, Bu, Cy, and Ph, as usedhere and throughout the specification refer to methyl, ethyl, propyl,butyl, cyclohexyl, and phenyl, respectively.

The foregoing Group 10 metal pro-catalyst components are commerciallyavailable or can be synthesized by techniques well known in the art.

As discussed above catalyst complex of Formula I can be formed in situby combining any of the Group 10 metal pro-catalysts with the desiredcatalyst system components in monomer. In cases where the Group 10 metalpro-catalyst already contains the desired ligand groups, thepro-catalyst is mixed in monomer along with the WCA salt or thealternative activators such as strong Lewis acids or Bronsted acids. TheWCA salt, strong Lewis acid or Bronsted acid serves as the an activatorfor the pro-catalyst in the presence of monomer. The in situ reactionsfor preparing the catalysts of Formula I generally follow the sameconditions and reaction schemes as outlined for the preparation of thepreformed single component catalysts, the principal difference beingthat the catalysts are formed in monomer in lieu of solvent and that apolymer product is formed.

Leaving Groups

A′ represents an anionic leaving group that can be readily displaced bythe weakly coordinating anion that is provided by the WCA salt. Theleaving group forms a salt with the cation on the WCA salt. Leavinggroup A′ is selected from halogen (i.e., Br, Cl, I, and F), nitrate,triflate (trifluoromethanesulfonate), triflimide(bistrifluoromethanesulfonimide), trifluoroacetate, tosylate, AlBr₄ ⁻,AlF₄ ⁻, AlCl₄ ⁻, AlF₃O₃SCF₃ ⁻, AsCl₆ ⁻, SbCl₆ ⁻, SbF₆ ⁻, PF₆ ⁻, BF₄ ⁻,ClO₄ ⁻, HSO₄ ⁻, carboxylates acetates, acetylacetonates, carbonates,aluminates, and borates.

In another embodiment the leaving group can be a hydrocarbyl group orhalogenated hydrocarbyl group when a Brønsted acid based WCA salt isutilized as the activator. In this embodiment the activator protonatesthe hydrocarbyl or halogenated hydrocarbyl forming a neutral moiety. Theleaving group moiety is, in one embodiment, selected from the hydride,linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,C₅-C₁₀ cycloalkyl, and C₆-C₁₀ aryl. The cycloalkyl and aryl moieties canoptionally be substituted with a halogen substituent selected frombromine, chlorine, fluorine, and iodine. In one embodiment, the halogenis fluorine. In this embodiment, A′ is protonated to yield the neutralmoiety A′H. Methyl and pentafluorophenyl groups are representativeexamples of leaving groups under this embodiment.

Halogen leaving groups include chlorine, iodine, bromine and fluorine.The acetates include groups of the formula R^(38′)C(O)O⁻, and thecarbonates include groups of the formula R^(38′)OC(O)O⁻, wherein R^(38′)represents linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅haloalkyl (in one embodiment, the haloalkyl contains only fluorine),linear or branched C₁-C₅ alkenyl, C₆-C₁₂ aryl, optionallymonosubstituted or independently multisubstituted with linear orbranched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl, and halogen(in one embodiment, fluorine).

The aluminate and borate leaving groups can be represented by theformulae M′(R^(39′))₄ ⁻, M′(GR^(39′))₄ ⁻, M′(—C≡CPh)₄ ⁻, or a moietyrepresented by the following structures:

wherein G is a sulfur or oxygen atom Ph represents phenyl andsubstituted phenyl as defined below, and R^(39′) independentlyrepresents linear or branched C₁-C₁₀ alkyl, linear or branched C₁-C₁₀chloro- or bromoalkyl, C₅-C₁₀ cycloalkyl, substituted and unsubstitutedaryl (in one embodiment, phenyl and substituted phenyl), substituted andunsubstituted C₇-C₂₀ aralkyl (in one embodiment, phenylalkyl andsubstituted phenylalkyl). By substituted is meant that the aryl orphenyl groups can contain one or more of linear or branched C₁-C₅ alkyl,linear or branched C₁-C₅ haloalkyl, chlorine, and bromine substituents,and combinations thereof.

Representative aluminate groups include but are not limited totetraphenoxyaluminate, tetrakis(cyclohexanolato)aluminate,tetraethoxyaluminate, tetramethoxyaluminate,tetrakis(isopropoxy)aluminate, tetrakis(2-butanolato)aluminate,tetrapentyloxyaluminate, tetrakis(2-methyl-2-propanolato)aluminate,tetrakis(nonyloxy)aluminate, andbis(2-methoxyethanolate-O,O′)bis(2-methoxyethanolate-O′)aluminate,tetrakis(phenyl)aluminate, tetrakis(p-tolyl)aluminate,tetrakis(m-tolyl)aluminate, tetrakis(2,4-dimethylphenyl)aluminate, andtetrakis(3,5-dimethylphenyl)aluminate.

Representative borate groups include tetraphenylborate,tetrakis(4-methylphenyl)borate, tetrakis(4-chlorophenyl)borate,tetrakis(4-bromophenyl)borate, tetrakis(2-bromo-4-chlorophenyl)borate,butyltriphenylborate, tetrakis(4-methoxyphenyl)borate,tetrakis(phenylethynyl)borate, bis(1,2-benzenediolato)borate,triphenyl(phenylethynyl)borate, bis(tetrafluorobenzenediolate)borate,bis(tetrachlorobenzenediolate)borate,bis(tetrabromobenzenediolate)borate,bis(1,1′-biphenyl-2,2′-diolato)borate, tetrakis(thiophenolyl)borate,bis(3,5-di-tert-butylbenzenediolate)borate,tetrakis(2,4-dimethylphenyl)borate, tetrakis(p-tolyl)borate,tetrakis(3,5-dimethylphenyl)borate, and tetrakis(m-tolyl)borate.

In addition to the anionic leaving groups described above, A′ can alsobe selected from highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl containing anions of the formulae (R^(40′)SO₂)₂CH⁻,(R^(40′)SO₂)₃C⁻, and (R^(40′)SO₂)₂N⁻, wherein R^(40′) independentlyrepresents linear or branched C₁-C₂₀ highly fluorinated andperfluorinated alkyl, C₅-C₁₅ highly fluorinated and perfluorinatedcycloalkyl, and highly fluorinated and perfluorinated C₆-C₂₂ aryl.Optionally, the alkyl and cycloalkyl groups can contain a heteroatom inthe chain of cyclic structure, respectively. In one embodiment, theheteroatoms include divalent (non-peroxidic) oxygen (i.e., —O—),trivalent nitrogen, and hexavalent sulfur. Any two of R^(40′) can betaken together to form a ring. When R^(40′) is a cycloalkyl substituent,a heterocycloalkyl substituent, or is taken with another R^(40′) groupto form a ring, the ring structures, in one embodiment, contain 5 or 6atoms, 1 or 2 of which can be heteroatoms.

In the above formulae the term highly fluorinated means that at least 50percent of the hydrogen atoms bonded to the carbon atoms in the alkyl,cycloalkyl, and aryl moieties are replaced by fluorine atoms. In oneembodiment, at least 2 out of every 3 hydrogen atoms on the alkyl,cycloalkyl, and aryl moieties under R^(40′) are replaced by fluorine. Inanother embodiment, at least 3 out of every 4 hydrogen atoms arereplaced by fluorine. In yet another embodiment, all of the hydrogenatoms on the R^(40′) substituent are replaced by fluorine to give theperfluorinated moiety. In addition to or in lieu of fluorine atomsubstitution on the aryl ring(s), the aryl groups can contain linear orbranched C₁-C₁₀ highly fluorinated and perfluorinated alkyl groups, suchas, for example, trifluoromethyl. In embodiments where hydrogen atomsremain on the alkyl, cycloalkyl, and aryl moieties, a portion or all ofthe remaining hydrogen atoms can be replaced with bromine and/orchlorine atoms.

Representative highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl containing anions of the foregoing formulae include but arenot limited to (C₂F₅SO₂)₂N⁻, (C₄F₉SO₂)₂N⁻, (CF₃SO₂)₂N⁻,(CF₃SO₂)(C₄F₉SO₂)N⁻, ((CF₃)₂NC₂F₄SO₂)₂N⁻, (C₆F₅SO₂)(CF₃SO₂)N⁻,(CF₃SO₂)(CHF₂SO₂)N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻, (C₃F₇SO₂)₂N⁻,((CF₃)₂(F)CSO₂)₂N⁻, (C₄F₈(CF₃)₂NSO₂)₂N⁻, (C₈F₁₇SO₂)₃C⁻, (CF₃SO₂)₃C⁻,(CF₃SO₂)₂CH⁻, (C₄F₉SO₂)₃C⁻, (CF₃SO₂)₂(C₄F₉SO₂)C⁻,((CF₃)₂NC₂F₄SO₂)C(SO₂CF₃)₂ ⁻, (3,5-bis(CF₃)C₆H₃)SO₂N(SO₂CF₃)⁻,(C₆F₅SO₂)C(SO₂CF₃)₂ ⁻, and the structures exemplified below:

Additional highly fluorinated and perfluorinated alkylsulfonyl andarylsulfonyl anions suitable as leaving groups are described in Turowskyand Seppelt, Inorganic Chemistry, 1988, 27, 2135-2137, and in U.S. Pat.Nos. 4,387,222; 4,505,997; 5,021,308; 5,072,040; 5,162,177; and5,273,840 the disclosures of which are hereby incorporated by reference.

WCA SALTS

The salt of the weakly coordinating anion employed in the process of thepresent invention can be represented by the formula[C(L″)_(z)]_(b)[WCA]_(d), wherein C represents a proton (H⁺), analkaline earth metal cation, a transition metal cation or an organicgroup containing cation, L″ and WCA, are as defined above, z is aninteger from 0 to 8, and b and d represent the number of times thecation complex and weakly coordinating counteranion complex (WCA),respectively, are taken to balance the electronic charge on the overallsalt complex.

The alkali metal cations include Group 1 metals selected from lithium,sodium, potassium, rubidium, and cesium. In one embodiment, the Group 1metal cations are lithium, sodium and potassium.

The alkali earth metal cations include Group 2 metals selected fromberyllium, magnesium, calcium, strontium, and barium. In one embodiment,the Group 2 metal cations are magnesium, calcium, strontium, and barium.The transition metal cation is selected from zinc, silver, and thallium.

The organic group cation is selected from ammonium, phosphonium,carbonium and silylium cations, i.e., [NHR^(41′) ₃]⁺, [NR^(41′) ₄]⁺,[PHR^(41′) ₃], [PR^(41′) ₄], [R^(41′) ₃C]⁺, and [R^(41′) ₃Si]⁺, whereR^(4′) independently represents a hydrocarbyl, silylhydrocarbyl, orperfluorocarbyl group, each containing 1 to 24 carbon atoms, (or inanother embodiment, from 1 to 12 carbons) arranged in a linear,branched, or ring structure. By perfluorocarbyl is meant that all carbonbonded hydrogen atoms are replaced by a fluorine atom. Representativehydrocarbyl groups include but are not limited to linear or branchedC₁-C₂₀ alkyl, C₃-C₂₀ cycloalkyl, linear or branched C₂ to C₂₀ alkenyl,C₃-C₂₀ cycloalkenyl, C₆-C₂₄ aryl, and C₇-C₂₄ aralkyl, and organometalliccations. The organic cations are selected from trityl,trimethylsilylium, triethylsilylium, tris(trimethylsilyl)silylium,tribenzylsilylium, triphenylsilylium, tricyclohexylsilylium,dimethyloctadecylsilylium, and triphenylcarbenium (i.e., trityl). Inaddition to the above cation complexes ferrocenium cations such as[(C₅H₅)₂Fe]⁺ and [(C₅(CH₃))₂Fe]⁺ are also useful as the cation in theWCA salts of the invention.

Examples of WCA salts having a weakly coordinating anion described underFormula II include but are not limited to

lithium tetrakis(2-fluorophenyl)borate, sodiumtetrakis(2-fluorophenyl)borate, silver tetrakis(2-fluorophenyl)borate,thallium tetrakis(2-fluorophenyl)borate, lithiumtetrakis(3-fluorophenyl)borate, sodium tetrakis(3-fluorophenyl)borate,silver tetrakis(3-fluorophenyl)borate, thalliumtetrakis(3-fluorophenyl)borate, ferroceniumtetrakis(3-fluorophenyl)borate, ferroceniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(4-fluorophenyl)borate, sodium tetrakis(4-fluorophenyl)borate,silver tetrakis(4-fluorophenyl)borate, thalliumtetrakis(4-fluorophenyl)borate, lithiumtetrakis(3,5-difluorophenyl)borate, sodiumtetrakis(3,5-difluorophenyl)borate, thalliumtetrakis(3,5-difluorophenyl)borate, trityltetrakis(3,5-difluorophenyl)borate, 2,6-dimethylaniliniumtetrakis(3,5-difluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium(diethylether)tetrakis(pentafluorophenyl)borate, lithium(diethyl ether)_(2.5)tetrakis(pentafluorophenyl)borate (also referred to herein as LiFABA),lithium tetrakis(2,3,4,5-tetrafluorophenyl)borate, lithiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, lithiumtetrakis(1,2,2-trifluoroethylenyl)borate, lithiumtetrakis(3,4,5-trifluorophenyl)borate, lithiummethyltris(perfluorophenyl)borate, lithiumphenyltris(perfluorophenyl)borate, lithiumtris(isopropanol)tetrakis(pentafluorophenyl)borate, lithiumtetrakis(methanol)tetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, tris(toluene)silvertetrakis(pentafluorophenyl)borate, tris(xylene)silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, trityltetrakis(4-triisopropylsilyltetrafluorophenyl)borate, trityltetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, 2,6-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate lithium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodium(triphenylsiloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(2,3,4,5-tetrafluorophenyl)borate, sodiumtetrakis(3,4,5,6-tetrafluorophenyl)borate, sodiumtetrakis(1,2,2-trifluoroethylenyl)borate, sodiumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, sodiumphenyltris(perfluorophenyl)borate, ithalliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, thalliumtetrakis(3,4,5,6-tetrafluorophenyl)borate, thalliumtetrakis(1,2,2-trfluoroethylenyl)borate, thalliumtetrakis(3,4,5-trifluorophenyl)borate, sodiummethyltris(perfluorophenyl)borate, thalliumphenyltris(perfluorophenyl)borate, trityltetrakis(2,3,4,5-tetrafluorophenyl)borate, trityltetrakis(3,4,5,6-tetrafluorophenyl)borate, trityltetrakis(1,2,2-trifluoroethylenyl)borate, trityltetrakis(3,4,5-trifluorophenyl)borate, tritylmethyltris(pentafluorophenyl)borate, tritylphenyltris(perfluorophenyl)borate, silvertetrakis[3,5-bis(trifluoromethyl)phenyl]borate,silver(toluene)tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, thalliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, lithium(hexyltris(pentafluorophenyl)borate, lithiumtriphenylsiloxytris(pentafluorophenyl)borate,lithium(octyloxy)tris(pentafluorophenyl)borate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,sodium(octyloxy)tris(pentafluorophenyl)borate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, potassiumtetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate,potassium(octyloxy)tris(pentafluorophenyl)borate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, magnesiumtetrakis(pentafluorophenyl)borate, magnesiummagnesium(octyloxy)tris(pentafluorophenyl)borate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, calciumtetrakis(pentafluorophenyl)borate, calcium(octyloxy)tris(pentafluorophenyl)borate, calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithiumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,sodiumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,silvertetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,thalliumtetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate,lithiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,lithiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,sodiumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,silvertetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,thalliumtetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate,trimethylsilylium tetrakis(pentafluorophenyl)borate, trimethylsilyliumetherate tetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate, triphenylsilyliumtetrakis(pentafluorophenyl)borate, tris(mesityl)silyliumtetrakis(pentafluorophenyl)borate, tribenzylsilyliumtetrakis(pentafluorophenyl)borate, trimethylsilyliummethyltris(pentafluorophenyl)borate, triethylsilyliummethyltris(pentafluorophenyl)borate, triphenylsilyliummethyltris(pentafluorophenyl)borate, tribenzylsilyliummethyltris(pentafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, tribenzylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, trimethylsilyliumtetrakis(3,4,5-trifluorophenyl)borate, tribenzylsilyliumtetrakis(3,4,5-trifluorophenyl)aluminate, triphenylsilyliummethyltris(3,4,5-trifluorophenyl)aluminate, triethylsilyliumtetrakis(1,2,2-trifluoroethenyl)borate, tricyclohexylsilyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, dimethyloctadecylsilyliumtetrakis(pentafluorophenyl)borate, tris(trimethyl)silyl)silyliummethyltri(2,3,4,5-tetrafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(pentafluorophenyl)borate,2,2′-dimethyl-1,1′-binaphthylmethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, lithiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, trityl(perfluorobiphenyl)fluoroaluminate,lithium(octyloxy)tris(pentafluorophenyl)aluminate, lithiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, sodiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate,sodium(octyloxy)teas(pentafluorophenyl)aluminate, sodiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, potassiumtetrakis(pentafluorophenyl)aluminate, trityltetrakis(pentafluorophenyl)aluminate, potassium(octyloxy)tris(pentafluorophenyl)aluminate, potassiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, magnesiumtetrakis(pentafluorophenyl)aluminate,magnesium(octyloxy)tris(pentafluorophenyl)aluminate, magnesiumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate, calciumtetrakis(pentafluorophenyl)aluminate, calcium(octyloxy)tris(pentafluorophenyl)aluminate, and calciumtetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate.

Examples of WCA salts having a weakly coordinating anion described underFormula III include but are not limited to LiB(OC(CF₃)₃)₄,LiB(OC(CF₃)₂(CH₃))₄, LiB(OC(CF₃)₂H)₄, LiB(OC(CF₃)(CH₃)H)₄,TIB(OC(CF₃)₃)₄, TIB(OC(CF₃)₂H)₄, TIB(OC(CF₃)(CH₃)H)₄,TIB(OC(CF₃)₂(CH₃))₄, (Ph₃C)B(OC(CF₃)₃)₄, (Ph₃C)B(OC(CF₃)₂(CH₃))₄,(Ph₃C)B(OC(CF₃)₂H)₄, (Ph₃C)B(OC(CF₃)(CH₃)H)₄, AgB(OC(CF₃)₃)₄,AgB(OC(CF₃)₂H)₄, AgB(OC(CF₃)(CH₃)H)₄, LiB(O₂C₆F₄)₂, TIB(O₂C₆F₄)₂,Ag(toluene)₂B(O₂C₆F₄)₂, and Ph₃CB(O₂C₆F₄)₂, LiB(OCH₂(CF₃)₂)₄,[Li(HOCH₃)₄]B(O₂C₆Cl₄)₂, [Li(HOCH₃)₄]B(O₂C₆F₄)₂,[Ag(toluene)₂]B(O₂C₆Cl₄)₂, LiB(O₂C₆Cl₄)₂, (LiAl(OC(CF₃)₂Ph)₄),(TIAl(OC(CF₃)₂Ph)₄), (AgAl(OC(CF₃)₂Ph)₄), (Ph₃CAl(OC(CF₃)₂Ph)₄,(LiAl(OC(CF₃)₂C₆H₄CH₃)₄), (ThAl(OC(CF₃)₂C₆H₄CH₃)₄),(AgAl(OC(CF₃)₂C₆H₄CH₃)₄), (Ph₃CAl(OC(CF₃)₂C₆H₄CH₃)₄), LiAl(OC(CF₃)₃)₄,ThAl(OC(CF₃)₃)₄, AgAl(OC(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₃)₄,LiAl(OC(CF₃)(CH₃)H)₄, TIAl(OC(CF₃)(CH₃)H)₄, AgAl(OC(CF₃)(CH₃)H)₄,Ph₃CAl(OC(CF₃)(CH₃)H)₄, LiAl(OC(CF₃)₂H)₄, TIAl(OC(CF₃)₂H)₄,AgAl(OC(CF₃)₂H)₄, Ph₃CAl(OC(CF₃)₂H)₄, LiAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,TIAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, AgAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-i-Pr)₄, LiAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,TIAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, AgAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-t-butyl)₄, LiAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,TIAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-SiMe₃)₄, LiAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,TIAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄, AgAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₄-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,TIAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,Ph₃CAl(OC(CF₃)₂C₆H₂-2,6-(CF₃)₂-4-Si-i-Pr₃)₄,LiAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, TIAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,AgAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄, Ph₃CAl(OC(CF₃)₂C₆H₃-3,5-(CF₃)₂)₄,LiAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, TIAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,AgAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄, Ph₃CAl(OC(CF₃)₂C₆H₂-2,4,6-(CF₃)₃)₄,LiAl(OC(CF₃)₂C₆F₅)₄, TIAl(OC(CF₃)₂C₆F₅)₄, AgAl(OC(CF₃)₂C₆F₅)₄, andPh₃CAl(OC(CF₃)₂C₆F₅)₄.

Examples of boratobenzene salts include but are not limited to[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borinyl lithium,[1,4-dihydro-4-methyl-1-(pentafluorophenyl)]-2-borinyltriphenylmethylium,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borinyl lithium,4-(1,1-dimethyl)-1,2-dihydro-1-(pentafluorophenyl)-2-borinyltriphenylmethylium, 1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borinyllithium, 1-fluoro-1,2-dihydro-4-(pentafluorophenyl)-2-borinyltriphenylmethylium,1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borinyllithium, and1-[3,5-bis(trifluoromethyl)phenyl]-1,2-dihydro-4-(pentafluorophenyl)-2-borinyltriphenylmethylium.

Examples of WCA carborane and halocarborane salts include but are notlimited to silver dodecahydro-1-carbadodecaborate, LiCB₁₁(CH₃)₁₂,LiCB₁₁H₁₂, (Me₃NH)[CB₁₁H₁₂], (Me₄N)[1-C₂H₅CB₁₁H₁₁],(Me₄N)[1-Ph₃SiCB₁₁H₁₁], (Me₄N)[1-CF₃CB₁₁H₁₁], Cs[12-BrCB₁₁H₁₁],Ag[12-BrCB₁₁H₁₁], Cs[7,12-Br₂CB₁₁H₁₀], Cs[12-ClCB₁₁H₁₁],Cs[7,12-Cl₂CB₁₁H₁₀], Cs[1-H—CB₁₁F₁₁], Cs[1-CH₃—CB₁₁F₁₁],(i-Pr₃)Si[1-CF₃—CB₁₁F₁₁], Li[12-CB₁₁H₁₁F], Li[7,12-CB₁₁H₁₁F₂],Li[7,9,12-CB₁₁H₁₁F₃], (i-Pr₃)Si[CB₁₁H₆Br₆], Cs[CB₁₁H₆Br₆], Li[6-CB₉H₉F],Li[6,8-CB₉H₈F₂], Li[6,7,8-CB₉H₇F₃], Li[6,7,8,9-CB₉H₆F₄],Li[2,6,7,8,9-CB₉H₅F₅], Li[CB₉H₅Br₅], Ag[CB₁₁H₆Cl₆], TI[CB₁₁H₆Cl₆],Ag[CB₁₁H₆F₆], TI[CB₁₁H₆F₆], Ag[CB₁₁H₆I₆], Tl[CB₁₁H₆I₆], Ag[CB₁₁H₆Br₆],Tl[CB₁₁H₆Br₆], Li[6,7,9,10,11,12-CB₁₁H₆F₆], Li[2,6,7,8,9,10-CB₉H₅F₅],Li[1-H—CB₉F₉], Tl[12-CB₁₁H₁₁(C₆H₅)], Ag[1-C₆F₅—CB₁₁H₅Br₆], Li[CB₁₁Me₁₂],Li[CB₁₁(CF₃)₁₂], Li[CB₁₁H₆I₆], Li[CB₉H₅Br₅], Li[Co(B₉C₂H₁₁)₂],Li[CB₁₁(CH₃)₁₂], Li[CB₁₁(C₄H₉)₁₂], Li[CB₁₁(C₆H₁₃)₁₂], Na[Co(C₂B₉H₁₁)₂],and Na[Co(Br₃C₂B₉H₈)₂]. Additional halocarborane salts are disclosed inInternational Patent Publication WO 98/43983, which is herebyincorporated by reference.

Monomers

The catalysts of the present invention are suitable for the preparationof a wide range of polymers comprising cyclic repeating units. Thecyclic polymers are prepared by the addition polymerization of apolycycloolefin monomer(s) in the presence of a catalytic amount of acatalyst of Formula I or the pro-catalyst components described above.The monomer(s) can be polymerized via solution or mass polymerizationtechniques. As stated herein the terms “polycycloolefin,” “polycyclic,”and “norbornene-type” monomer are used interchangeably and mean that themonomer contains at least one norbornene moiety as shown below:

where X′″ represents oxygen, nitrogen with hydrogen or a C₁ to C₁₀ alkyllinear or branched being bonded thereto, sulfur or a methylene group ofthe formula —(CH₂)_(n′)— where n′ is an integer of 1 to 5.

The simplest polycyclic monomer of the invention is the bicyclicmonomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene.The term norbornene-type monomer is meant to include norbornene,substituted norbornene(s), and any substituted and unsubstituted highercyclic derivatives thereof so long as the monomer contains at least onenorbornene-type or substituted norbornene-type moiety. In oneembodiment, the substituted norbornene-type monomers and higher cyclicderivatives thereof contain a pendant hydrocarbyl substituent(s) or apendant functional substituent(s) containing an oxygen atom. In oneembodiment, the norbornene-type or polycycloolefin monomers arerepresented by the structure below:

wherein each X′″ is independently defined as above, “a” represents asingle or double bond, R¹ to R⁴ independently represent a hydrogen,hydrocarbyl or functional substituent, m is an integer from 0 to 5, andwhen “a” is a double bond one of R¹, R² and one of R³, R⁴ are notpresent.

When the substituent is a hydrocarbyl group, R¹ to R⁴ can be ahalohydrocarbyl, or perhalohydrocarbyl group, or even a perhalocarbylgroup (e.g., a trifluormethyl group). In one embodiment, R¹ to R⁴independently represent hydrocarbyl, halogenated hydrocarbyl andperhalogenated hydrocarbyl groups selected from hydrogen, linear orbranched C₁-C₁₀ alkyl, linear or branched, C₂-C₁₀ alkenyl, linear orbranched C₂-C₁₀ alkynyl, C₄-C₁₂ cycloalkyl, C₄-C₁₂ cycloalkenyl, C₆-C₁₂aryl, and C₇-C₂₄ aralkyl, R¹ and R² or R³ and R⁴ can be taken togetherto represent a C₁-C₁₀ alkylidenyl group. Representative alkyl groupsinclude but are not limited to methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl,octyl, nonyl, and decyl. Representative alkenyl groups include but arenot limited to vinyl, allyl, butenyl, and cyclohexenyl. Representativealkynyl groups include but are not limited to ethynyl, 1-propynyl,2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groupsinclude but are not limited to cyclopentyl, cyclohexyl, and cyclooctylsubstituents. Representative aryl groups include but are not limited tophenyl, naphthyl, and anthracenyl. Representative aralkyl groups includebut are not limited to benzyl, and phenethyl. Representative alkylidenylgroups include methylidenyl, and ethylidenyl, groups.

In one embodiment, the perhalohydrocarbyl groups include perhalogenatedphenyl and alkyl groups. The halogenated alkyl groups useful in theinvention are partially or fully halogenated and are linear or branched,and have the formula C_(z)X″_(2z+1) wherein X″ is independently ahalogen as set forth above or a hydrogen and z is selected from aninteger of 1 to 20. In another embodiment, each X″ is independentlyselected from hydrogen, chlorine, fluorine and/or bromine. In yetanother embodiment, each X″ is independently either a hydrogen or afluorine.

In one embodiment, the perfluorinated substituents includeperfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl,perfluorobutyl, and perfluorohexyl. In addition to the halogensubstituents, the cycloalkyl, aryl, and aralkyl groups of the inventioncan be further substituted with linear or branched C₁-C₅ alkyl andhaloalkyl groups, aryl groups and cycloalkyl groups.

When the pendant group(s) is a functional substituent, R¹ to R⁴independently represent a radical selected from(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃, —(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—CH₃,—(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(CH₃)₃, —(CH₂)_(n)—C(CF₃)₂—OH,—(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl, —(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵,—(CH₂)_(n)—OC(O)R⁵, —(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵,—(CH₂)_(n)Si(R⁵)₃, —(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)—O—Si(R⁵)₃, and—(CH₂)_(n)C(O)OR⁶ wherein n independently represents an integer from 0to 10 and R⁵ independently represents hydrogen, linear or branchedC₁-C₂₀ alkyl, linear or branched C₁-C₂₀ halogenated or perhalogenatedalkyl, linear or branched C₂-C₁₀ alkenyl, linear or branched C₂-C₁₀alkynyl, C₅-C₁₂ cycloalkyl, C₆-C₁₄ aryl, C₆-C₁₄ halogenated orperhalogenated aryl, and C₇-C₂₄ aralkyl. Representative hydrocarbylgroups set forth under the definition of R⁵ are the same as thoseidentified above under the definition of R¹ to R⁴. As set forth aboveunder R¹ to R⁴ the hydrocarbyl groups defined under R⁵ can behalogenated and perhalogenated. For example, when R⁵ is C₁-C₂₀halogenated or perhalogenated alkyl, R⁵ can be represented by theformula C_(z)X″_(2z+1), wherein z and X″ are defined as above, and atleast one X″ on the alkyl group must be a halogen (e.g., Br, Cl, or F).It is to be recognized that when the alkyl group is perhalogenated, allX″ substituents are halogenated. Examples of perhalogenated alkyl groupsinclude, but are not limited to, trifluoromethyl, trichloromethyl,—C₇F₁₅, and —C₁₁F₂₃. Examples of perhalogenated aryl groups include, butare not limited to, pentachlorophenyl and pentafluorophenyl. The R⁶radical represents an acid labile moiety selected from —C(CH₃)₃,—Si(CH₃)₃, —CH(R⁷)OCH₂CH₃, —CH(R⁷)OC(CH₃)₃ or the following cyclicgroups:

wherein R⁷ represents hydrogen or a linear or branched (C₁-C₅) alkylgroup. The alkyl groups include methyl, ethyl, propyl, i-propyl, butyl,i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the abovestructures, the single bond line projecting from the cyclic groupsindicates the position where the cyclic protecting group is bonded tothe acid substituent. Examples of R⁶ radicals include1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl,3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, and 1-t-butoxyethyl.

The R⁶ radical can also represent dicyclopropylmethyl (Dcpm), anddimethylcyclopropylmethyl (Dmcp) groups which are represented by thefollowing structures:

In Structure VII above, R¹ and R⁴ together with the two ring carbonatoms to which they are attached can represent a substituted orunsubstituted cycloaliphatic group containing 4 to 30 ring carbon atomsor a substituted or unsubstituted aryl group containing 6 to 18 ringcarbon atoms or combinations thereof. The cycloaliphatic group can bemonocyclic or polycyclic. When unsaturated the cyclic group can containmonounsaturation or multiunsaturation. In one embodiment, theunsaturated cyclic group is a monounsaturated cyclic group. Whensubstituted, the rings contain monosubstitution or multisubstitutionwherein the substituents are independently selected from hydrogen,linear or branched C₁-C₅ alkyl, linear or branched C₁-C₅ haloalkyl,linear or branched C₁-C₅ alkoxy, halogen, or combinations thereof. R¹and R⁴ can be taken together to form the divalent bridging group,—C(O)—Q—(O)C—, which when taken together with the two ring carbon atomsto which they are attached form a pentacyclic ring, wherein Q representsan oxygen atom or the group N(R⁸), and R⁸ is selected from hydrogen,halogen, linear or branched C₁-C₁₀ alkyl, and C₆-C₁₈ aryl. Arepresentative structure is shown in below.

wherein each X′″ is independently defined as above and m is an integerfrom 0 to 5.

Deuterium enriched norbornene-type monomers wherein at least one of thehydrogen atoms on the norbornene-type moiety and/or one at least one ofthe hydrogen atoms on a pendant hydrocarbyl substituent described underR¹ to R⁴ have been replaced by a deuterium atom are contemplated withinthe scope of the present invention. In one embodiment, at least 40percent of the hydrogen atoms on the norbornene-type moiety and/or thehydrocarbyl substituent are replaced by deuterium. In anotherembodiment, at least about 50 percent of the hydrogen atoms on thenorbornene-type moiety and/or the hydrocarbyl substituent are replacedby deuterium. In yet another embodiment, at least about 60 percent ofthe hydrogen atoms on the norbornene-type moiety and/or the hydrocarbylsubstituent are replaced by deuterium. In one embodiment, the deuteratedmonomers are represented by the structure below:

wherein X′″ is defined as above, R^(D) is deuterium, “i” is an integerranging from 0 to 6, with the proviso that when “i” is 0, at least oneof R^(1D) and R^(2D) must be present, R¹ and R² independently representa hydrocarbyl or functional substituent as defined above, and R^(1D) andR^(2D) may or may not be present and independently represent a deuteriumatom or a deuterium enriched hydrocarbyl group containing at least onedeuterium atom. In one embodiment, the deuterated hydrocarbyl group isselected from linear or branched C₁-C₁₀ alkyl wherein at least 40percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium. In another embodiment, the deuterated hydrocarbyl group isselected from linear or branched C₁-C₁₀ alkyl wherein at least 50percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium. In yet another embodiment, the deuterated hydrocarbyl groupis selected from linear or branched C₁-C₁₀ alkyl wherein at least 60percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium.

Crosslinked polymers can be prepared by copolymerizing thenorbornene-type monomer(s) set forth under Structure VII above with amultifunctional norbornene-type crosslinking monomer(s). Bymultifunctional norbornene-type crosslinking monomer is meant that thecrosslinking monomer contains at least two norbornene-type moieties(norbornene-type double bonds), each functionality being polymerizablein the presence of the catalyst system of the present invention. Thecrosslinkable monomers include fused multicyclic ring systems and linkedmulticyclic ring systems. Examples of fused crosslinking agents areillustrated in structures below. For brevity, norbornadiene is includedas a fused multicyclic crosslinking agent and is considered to containtwo polymerizable norbornene-type double bonds.

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond. Representative monomers under the forgoing formulae are setforth below.

A linked multicyclic crosslinking agent is illustrated generically inStructure VIII below.

wherein “a” independently represents a single or double bond, mindependently is an integer from 0 to 5, R⁹ is a divalent radicalselected from divalent hydrocarbyl radicals, divalent ether radicals anddivalent silyl radicals, and n is equal to 0 or 1. By divalent is meantthat a free valence at each terminal end of the radical is attached to anorbomene-type moiety. In one embodiment, the divalent hydrocarbylradicals are alkylene radicals and divalent aromatic radicals. Thealkylene radicals are represented by the formula —(C_(d)H_(2d))— where drepresents the number of carbon atoms in the alkylene chain and is aninteger from 1 to 10. The alkylene radicals are, in one embodiment,selected from linear or branched (C₁-C₁₀) alkylene such as methylene,ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene,nonylene, and decylene. When branched alkylene radicals arecontemplated, it is to be understood that a hydrogen atom in thealkylene backbone is replaced with a linear or branched (C₁ to C₅) alkylgroup.

The divalent aromatic radicals are selected from divalent phenyl, anddivalent naphthyl radicals. The divalent ether radicals are representedby the group —R¹⁰—O—R¹⁰—, wherein R¹⁰ independently is the same as R⁹.Examples of specific linked multicyclic crosslinking agents arerepresented as in Structures VIIIa to VIIIc as follows.

In one embodiment, the crosslinking agent is selected from those shownbelow:

which is dimethyl bis[bicyclo[2.2.1]hept-2-ene-5-methoxy]silane (alsoreferred to herein as dimethyl bis(norbornene methoxy)silane),

where n is 1 to 4,

Some other types of norbornene-based crosslinking agents include, butare not limited to, those represented in formulae a-m below.

In another embodiment, fluorine-containing norbornene-based crosslinkers are used. For example, in one embodiment one or more of thefollowing fluorinated norbornene crosslinking agents can be utilized.

F—Crosslinking Agent II.

Norbornadiene may be employed as a crosslinking agent in this invention.In another embodiment, higher homologs are utilized. Norbornadiene canbe converted into higher homologs or Diels-Alder products using avariety of dimerization catalysts or heating it with cyclopentadiene. Inthe case of the crosslinking monomer norbornadiene dimer an alternativesynthesis is employed in which norbornadiene is coupled catalytically toyield a mixture of isomers of norbornadiene dimer as shown below:

The dimerization of norbornadiene is easily achieved by numerouscatalysts to yield a mixed composition of up to six isomers, i.e., Wu etal. U.S. Pat. No. 5,545,790). In one embodiment, the isomers are theexo-trans-exo, endo-trans-endo, andexo-trans-endo-1,4,4a,4b,5,8,8a,8b-octahydro-1,4:5,8-dimethanobiphenylene(“norbornadiene dimer” or “[NBD]₂”). In another embodiment, theexo-trans-exo norbornadiene dimer is utilized as a crosslinking agent.Heating norbornadiene dimer with dicyclopentadiene or cyclopentadienecan produce higher oligomers of norbornadiene dimer. Other crosslinkingagents are prepared by the reaction of cyclopentadiene with olefinscontaining two or more reactive olefins, e.g., cyclooctadiene,1,5-hexadiene, 1,7-octadiene, and tricycloheptatriene.

In one embodiment, the crosslinkable monomers are those containing tworeactive norbornene type moieties (containing two polymerizable doublebonds). In another embodiment, the monomer is5,5′-(1,2-ethanediyl)bisbicyclo[2.2.1]hept-2-ene (NBCH₂CH₂NB) preparedby the reaction of 5-(3-butenyl)bicyclo[2.2.1]hept-2-ene andcyclopentadiene via a Diels-Alder reaction. The higher homolog of5-(3-butenyl)bicyclo[2.2.1]hept-2-ene is also a co-monomer of choice,i.e.,2-(3-butenyl)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene.Similarly, 1, 4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12, 12a-dodecahydro-1,4:7, 10-dimethanodibenzo[a,e]cyclooctene is prepared in the Diels Alderreaction between 1, 4, 4a, 5, 6, 9, 10,10a-octahydro-1,4-methanobenzocyclooctene and cyclopentadiene. Thehigher homolog of between 1, 4, 4a, 5, 6, 9, 10,10a-octahydro-1,4-methanobenzocyclooctene is also a comonomer of choice,i.e.,1,4,4a,5,5a,6,7,10,11,11a,12,12a-dodecahydro-1,4:5,12-dimethanocycloocta[b]naphthalene.The symmetric and asymmetric trimers of cyclopentadiene are also usefulcrosslinking reagents, i.e., 4, 4a, 4b, 5, 8, 8a, 9,9a-octahydro-1,4:5,8-dimethano-1H-fluorene and 3a, 4, 4a, 5, 8, 8a, 9,9a-octahydro-4,9:5,8dimethano-1H-benz[f]indene, respectively. In yetanother embodiment, the monomer is obtained from the reaction ofcyclopentadiene and norbornadiene, i.e.,1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene. Divinylbenzene andexcess cyclopentadiene forms the symmetric crosslinking agent5,5′-(1,4-phenylene)bisbicyclo[2.2.1]hept-2-ene.

An economical route for the preparation of hydrocarbyl substituted andfunctionally substituted norbornene monomers relies on the Diels-Alderaddition reaction in which CPD or substituted CPD is reacted with asuitable dienophile at elevated temperatures to form the substitutednorbomene-type adduct generally shown by the following reaction scheme:

wherein R¹ to R⁴ independently represent hydrogen, hydrocarbyl, and/or afunctional group as previously described.

Other norbornene type adducts can be prepared by the thermal pyrolysisof dicyclopentadiene (DCPD) in the presence of a suitable dienophile.The reaction proceeds by the initial pyrolysis of DCPD to CPD followedby the Diels-Alder addition of CPD and the dienophile to give theadducts shown below:

wherein n represents the number of cyclic units in the monomer and R¹ toR⁴ independently represent hydrogen, hydrocarbyl, and/or a functionalgroup as previously defined. Norbornadiene and higher Diels-Alderadducts thereof similarly can be prepared by the thermal reaction of CPDand DCPD in the presence of an acetylenic reactant as shown below.

wherein n, R¹ and R² are as defined above.

Deuterium enriched norbornene-type monomers can be prepared by heatingDCPD in the presence of D₂O and a base such as NaOH to yield deuteratedCPD which in turn can be reacted with a dienophile (Eq. 1) or adeuterated dienophile (Eq. 2) to give the respective deuteratednorbornene containing a pendant deuterated hydrocarbyl substituent or apendant hydrocarbyl substituent. In another embodiment non-deuteratedCPD can be reacted with a deuterium enriched dienophile to yieldnorbornene containing a deuterium enriched hydrocarbyl pendant group(Eq. 3).

In Eq. 1 and Eq. 2 above, R¹ to R⁴, R^(1D) and R^(2D) are as previouslydefined, and i′ is an integer ranging from 1 to 6.

Examples of polymerizable norbomene-type monomers include but are notlimited to norbornene (bicyclo[2.2.1 ]hept-2-ene),5-ethylidenenorbornene, dicyclopentadiene,tricyclo[5.2.1.0^(2,6)]deca-8-ene,5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylic acid,5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene,5-ethoxycarbonylbicyclo[2.2.1]hept-2-ene,5-n-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-i-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-n-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-(2-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-(1-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene,5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-(4′-t-butylcyclohexyloxy)carbonylbicyclo[2.2.1]hept-2-ene,5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene,5-tetrahydrofuranyloxycarbonybicyclo[2.2.1]hept-2-ene,5-tetrahydropyranyloxycarbonylbicyclo[2.2.1]hept-2-ene,bicyclo[2.2.1]hept-2-ene-5-carboxylic acid,5-acetyloxybicyclo[2.2.1]hept-2-ene,5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-ethoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-n-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-i-propoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-n-bputoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(2-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(2-methylpropoxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-t-butoxycarbonyl bicyclo[2.2.1]hept-2-ene,5-methyl-5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-(4′-t-butylcyclohexyloxy)carbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-phenoxycarbonylbicycloo[2.2.1]hept-2-ene,5-methyl-5-etrahydrofuranyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-tetrahydropyranyloxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-acetyloxybicyclo[2.2.1]hept-2-ene,5-methyl-5-cyanobicyclo[2.2.1]hept-2-ene,5,6-di(methoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(ethoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(n-propoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(ipropoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(n-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(phenoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(tetrahydrofuranyloxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-di(tetrahydropyranyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, and5,6-dicarboxyanhydridebicyclo[2.2.1]hept-2-ene,8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-i-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(2-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(1-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-t-butoxycarbonyltetracyclo[4.4.0.1^(2.5).1^(7,10)]dodec-3-ene,8-cyclohexyoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(4′-t-butylcyclohexyloxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-phenoxycarbonyltetracycloo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-petrahydrofuranyloxyarbonyltetracyclo[4.4.0.1_(2,5).1^(7,10)]-3-dodecene,8-tetrahydropyranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-acetyloxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1_(7,10)]dodec-3-ene,8-methyl-8-i-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(2-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(1-methylpropoxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-t-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-cyclohexyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(4′-t-butylcyclohexyloxy)carbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-phenoxycarbonyltetracyclo[4.4.0.1^(2,5).1_(7,10)]dodec-3-ene,8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8-methyl-8-acetyloxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(methoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(ethoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(n-propoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(i-prooxycarbonylftetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(n-butoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(cyclohloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(t-butoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(cyclohexyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(phenoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-di(tetrahydrofuranyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8,9-di(tetrahydropyranyloxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene,8,9-dicarboxyanhydidetetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene-8-carboxylic acid,8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene-8-carboxylic acid,8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-ethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-difluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-pentafluoroethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-difluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-difluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-tris(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9,9-tetrafluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9,9-tetrakis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8-difluoro-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-difluoro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-trifluoromethoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,8,9-trifluoro-9-pentafluoropropoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-fluoro-8-pentafluoroethyl-9,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-chloro-8,9,9-trifluorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8,9-dichloro-8,9-bis(trifluoromethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-(2,2,2-trifluorocarboxyethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,8-methyl-8-(2,2,2-trifluorocarboxyethyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodec-3-ene,tricyclo[4.4.0.1^(2,5)]undeca-3-ene,tricyclo[6.2.1.0^(1,8)]undeca-9-ene,tetracyclo[4.4.0.1^(2,5).1^(7,10).0^(1,6)]dodec-3-ene,8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10).0^(1,6)]dodec-3-ene,8-ethylidenetetracyclo[4.4.0.1^(2,5).1^(7,12)]dodec-3-ene,8-ethylidenetetracyclo[4.4.0.1^(2,5).1^(7,10).0^(1,6)]dodec-3-ene,pentacyclo[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-4-ene,pentacyclo[7.4.0.1^(2,5).1^(9,12).0^(8,13)]pentadeca-3-ene,5-(n-hexyl)-bicyclo[2.2.1]hept-2-ene,5-(triethoxysily)bicyclo[2.2.1]]hept-2-ene, andbicyclo[2.2.1]hept-2-ene-5-methoxy diphenyl methyl silane (also referredto herein as diphenyl methyl (norbornene methoxy)silane).

Examples of polymerizable norbornene-type monomers include but are notlimited to, norbornene (bicyclo[2.2.1]hept-2-ene),5-methyl-2-norbornene, ethylnorbornene, propylnorbonrnene,isopropyinorbonrnene, butyinorbornene, isobutylnorbornene,pentyinorbornene, hexylnorbornene, heptyinorbonrnene, octylnorbornene,decyinorbornene, dodecylnorbornene, octadecylnorbornene,trimethoxysilyinorbonrnene, butoxynorbornene, p-tolyinorbornene,methylidene norbonrnene, phenylnorbornene, ethylidenenorbonrnene,vinyinorbonrnene, exo-dicyclopentadiene, endo-dicyclopentadiene,tetracyclododecene, methyltetracyclododecene,dimethyltetracyclododecene, ethyltetracyclododecene, ethylidenyltetracyclododecene, phenyltetracyclodecene, tetramers ofcyclopentadiene, propenylnorbornene,5,8-methylene-5a,8a-dihydrofluorene, cyclohexenylnorbornene,dimethanohexahydronaphthalene, endo,exo-5,6-dimethoxynorbonrnene,endo,endo-5,6-dimethoxynorbornene, 2,3-dimethoxynorbomadiene,5,6-bis(chloromethyl)bicyclo[2.2.1]hept-2-ene,5-tris(ethoxy)silylnorbornene,2-dimethylsilylbicyclo[2.2.1]hepta-2,5-diene,2,3-bistrifluoromethylbicyclo[2.2.1]hepta-2,5-diene,5-fluoro-5-pentafluoroethyl-6-,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene,5,6-difluoro-5-heptafluoroisopropyl-6-trifluoromethyl)bicyclo[2.2.1]hept-2-ene,2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0]dec-8-ene, and5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-a-naphthyl-2-norbornene,5,5-dimethyl-2-norbonrnene,1,4,4a,9,9a,10-hexahydro-9,10[1′,2′]-benzeno-1,4-methanoanthracene,indanylnorbornene (i.e., 1,4,4,9-tetrahydro-1,4-methanofluorene, thereaction product of CPD and indene),6,7,10,10-tetrahydro-7,10-methanofluoranthene (i.e., the reactionproduct of CPD with acenaphthalene),1,4,4,9,9,10-hexahydro-9,10[1′,2′]-benzeno-1,4-methanoanthracene,endo,endo-5,6-dimethyl-2-norbonrnene,endo,exo-5,6-dimethyl-2-norbonrnene, exo,exo-5,6-dimethyl-2-norbonrnene,1,4,4,5,6,9,10,13,14,14-decahydro-1,4-methanobenzocyclododecene (i.e.,reaction product of CPD and 1,5,9-cyclododecatriene),2,3,3,4,7,7-hexahydro-4,7-methano-1H-indene (i.e., reaction product ofCPD and cyclopentene), 1,4,4,5,6,7,8,8-octahydro-1,4-methanonaphthalene(i.e., reaction product of CPD and cyclohexene),1,4,4,5,6,7,8,9,10,10-decahydro-1,4-methanobenzocyclooctene (i.e.,reaction product of CPD and cyclooctene), and1,2,3,3,3,4,7,7,8,8,decahydro-4,7-methanocyclopent[a]indene.

In another embodiment of the invention the polymer can be crosslinkedduring a post polymerization curing step (latent crosslinking). In thisembodiment a norbornene-type monomer containing a pendant postcrosslinkable functional group is copolymerized into the polycyclicbackbone whereupon the functional group is subsequently crosslinked viawell known techniques. By post crosslinkable functional group is meantthat the functional group is inert to the initial polymerizationreaction but is receptive to subsequent chemical reactions to effect thecrosslinking of adjacent polymer chains. Suitable post crosslinkablemonomers are set forth under Structure VII wherein at least one of R¹ toR⁴ is selected from linear or branched C₂-C₁₀ alkenyl, C₄-C₁₀cycloalkenyl, —(CH₂)_(n)Si(OR⁵)₃, wherein n and R⁵ are as defined above,R¹ and R² or R³ and R⁴ can be taken together to represent a C₁-C₁₀alkylidenyl radical, fused cyclic groups wherein R¹ and R⁴ takentogether with the two ring carbon atoms to which they are attached forman unsaturated C₄ to C₈ ring. In one embodiment, post crosslinkablealkenyl functional groups include vinyl, butenyl, and cyclohexyl. In oneembodiment, alkylidenyl groups include methylidenyl and ethylidenylsubstituents. In one embodiment, alkoxysilyl groups includetrimethoxysilyl and triethoxysilyl moieties. In one embodiment,crosslinking agents containing fused multicyclic ring systems includedicyclopentadiene (DCPD) and unsymmetrical trimer of cyclopentadiene(CPD). Some exemplary latent corsslinking agents include, but are notlimited to, the formulae shown below:

where R_(h) represents a non-halogenated, halogenated or perhalogenatedgroup such as CnQ″_(2n+1), n is an integer from 1 to 10, and Q″represents a hydrogen or a halogen (e.g., Br, Cl, or F).

The latent crosslinkable pendant groups can be reacted via a varietychemistries known to initiate the reaction of the various functionalgroups. For example, the alkenyl, cycloalkenyl, and alkylidenyl groupsset forth under the definition R¹ to R⁵ of Structure VII above can becrosslinked via a free radical mechanism. The alkoxysilyl groups can becrosslinked via a cationic reaction mechanism. Representative monomersthat contain post crosslinkable functional groups are represented below.

In the latent crosslinking embodiment of the invention the crosslinkingreaction step can be induced by a free radical initiator. Suitableinitiators are those that can be activated thermally or photochemically.The initiator can be added to the reaction medium and the polymerizationof the monomer mixture is allowed to proceed to completion. If thelatent initiator is present during polymerization, then a keyconsideration is that the radical generating compound employed be stable(does not decompose) at the polymerization temperature of the monomericreaction medium. Altematively, the latent initiator can be added to asolution of the polymer in an appropriate solvent after thepolymerization has been completed. When utilizing thermally activatedfree radical generators or embodiments utilizing photo-acid generators,latent crosslinking is induced by exposing the polymer medium totemperatures above the decomposition temperature of the free radicalgenerating compound. In embodiments utilizing photoinitiated freeradical generators, latent crosslinking is induced by exposing thepolymer medium to a radiation source such as e-beam and UV radiation.Suitable free radical generator compounds (crosslinking agents) includethe organic peroxides and aliphatic azo compounds. The aliphatic azocompounds are suitable initiators for the thermal and photochemicalactivated crosslinking embodiments of the invention, while the organicperoxides are suitable for use in as thermally activated initiatorsonly. The amount of crosslinking agent employed ranges from about 0.005part by weight to about 5.0 parts by weight based on 100 parts by weightof monomer in the reaction medium.

Suitable organic peroxide include, but are not limited to, dibenzoylperoxide, di(2,4-dichlorobenzoyl)peroxide, diacetyl peroxide,diisobutyryl peroxide, dilauroyl peroxide, t-butylperbenzoate,t-butylperacetate, 2,5-di(benzoylperoxy)-1,2-dimethylhexane, di-t-butyldiperoxyazelate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroctoate,2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane,t-butylperoxyneodecanoate, ethyl 3,3-di(t-butylperoxy)butyrate,2,2-di(t-butylperoxy)butane, 1,1-di(t-butylperoxy)cyclohexane,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,2,5-di(t-butylperoxy)-2,5-dimethylhex-3-yne, di-t-butyl peroxide,2,5-di(t-butylperoxy)-2,5-dimethylhexane, dicumyl peroxide, n-propylperoxydicarbonate, i-propyl peroxydicarbonate, cyclohexylperoxydicarbonate, and acetyl peroxydicarbonate.

Suitable azo compounds include, but are not limited to,2,2′-azobis[2,4-dimethyl]pentane,2-(t-butylazo)-4-methoxy-2,4-dimethylpentanenitrile,2,2′-azobis(i-butyronitrile), 2-(t-butylazo)-2,4-dimethylpentanenitrile,2-(t-butylazo)i-butyronitrile, 2-(t-butylazo)-2-methylbutanenitrile,1,1-azobis-cyclohexanecarbonitrile,1-(t-amylazo)cyclohexanecarbonitrile, and1-(t-butylazo)cyclohexanecarbonitrile.

Suitable photo-initiators for free-radical crosslinking include, but arenot limited to, benzoin ethyl ether, diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide, 4,4′-bis(diethylamino)benzophenone,4,4′-bis(dimethylamino)benzophenone and 4-(dimethylamino)benzophenone.

Suitable photo-initiators for cationic crosslinking include, but are notlimited to, onium salts, halogenated organic compounds, quinone diazidecompounds, α,α-bis(sulfonyl)diazomethane compounds,α-carbonyl-α-sulfonyl diazomethane compounds, sulfone compounds, organicacid ester compounds, organic acid amide compounds, organic acid imidecompounds, etc. Actual examples of onium salts are unsubstituted orsymmetrically or asymmetrically substituted alkyl groups, alkenylgroups, aralkyl groups, aromatic groups, diazonium salts withheterocyclic groups, ammonium salts, iodonium salts, sulfonium salts,phosphonium salts, arsonium salts, oxonium salts, etc. There are norestrictions to counter anions of these onium salts as long as they arecompounds that can form counter anions. Examples are boric acid, arsenicacid, phosphoric acid, antimonic acid, sulfonic acid, carboxylic acid,and their halides. There are no special restrictions to the halogenatedorganic compound as long as they are halides or organic compounds, and avariety of conventional compounds can be employed. Actual examplesinclude halogen-containing oxadiazole compounds, halogen-containingtriazine compounds, halogen-containing acetophenone compounds,halogen-containing benzophenone compounds, halogen-contianing sulfoxidecompounds, halogen-containing sulfone compounds, halogen-containingthiazole compounds, halogen-containing oxazole compounds,halogen-containing triazole compounds, haloge-containing 2-pyronecompounds, is halogen-containing aliphatic hydrocarbon compounds,halogen-containing aromatic compounds, other halogen-containingheterocyclic compounds, sulfonyl halide compounds, etc. Actual examplesof o-quinone diazide compounds are 1,2-benzoquinone diazido-4-sulfonicacid ester, 1,2-naphthoquinone diazido-4-sulfonic acid ester,1,2-naphthoquinone diazido-5-sulfonic acid ester, 1,2-naphthoquinonediazido-6-sulfonic acid ester, 2,1-naphthoquinone diazido-4-sulfonicacid ester, 2,1-naphthoquinone diazido-5-sulfonic acid ester,2,1-naphthoquinone diazido-6-sulfonic acid ester, other quinone diazidoderivative sulfonic acid esters, 1,2-benzoquinone diazido-4-sulfonicacid chloride, 1,2-naphthoquinone diazido-4-sulfonic acid chloride,1,2-naphthoquinone diazido-5-sulfonic acid chloride, 1,2-naphthoquinonediazido-6-sulfonic acid chloride, 2,1-naphthoquinone diazido-4-sulfonicacid chloride, 2,1-naphthoquinone diazido-5-sulfonic acid chloride,2,1-naphthoquinone diazido-6-sulfonic acid chloride, and other quinonediazide derivative sulfonic acid chlorides. Examples ofα,α-bis(sulfonyl)diazomethane compounds are unsubstituted orsymmetrically or asymmetrically substitutedα,α-bis(sulfonyl)diazomethane with alkyl groups, alkenyl groups, aralkylgroups, aromatic groups, or heterocyclic groups, etc. Actual examples ofα-carbonyl-α-sulfonyl diazomethane compounds are unsubstituted orsymmetrically or asymmetrically substituted α-carbonyl-α-sulfonyldiazomethane with alkyl groups, alkenyl groups, arakyl groups, aromaticgroups, or heterocyclic groups. Actual examples of sulfone compounds arenon-substituted or symmetrically or asymmetrically substituted sulfonecompounds or disulfone compounds with alkyl groups, alkenyl groups,aralkyl groups, aromatic groups or heterocyclic groups. Actual examplesof organic acid esters are unsubstituted or symmetrically orasymmetrically substituted carboxylic acid esters, sulfonic acid esters,etc., with alkyl groups, alkenyl groups, aralkyl groups, aromatic groupsor heterocyclic groups. Actual examples of organic acid amide groups areunsubstituted or symmetrically or asymmetrically substituted carboxylicacid amides, sulfonic acid amides, etc., with alkyl groups, alkenylgroups, aralkyl groups, aromatic groups or heterocyclic groups. Actualexamples of organic imides are unsubstituted or symmetrically orasymmetrically substituted carboxylic acid imides, sulfonic acid imides,etc., with alkyl groups, alkenyl groups, aralkyl groups, aromatic groupsor heterocyclic groups. One or more of the photo-initiators can beutilized in the present invention.

When a latent initiator is present during polymerization or in thepolymerization medium, the decomposition temperatures of the foregoingfree radical generator compounds are well known in the art and can beselected on the basis of the polymerization temperatures employed ininitial reaction. In other words the initiator compound must be stableat the polymerization temperatures so it is available for the postpolymerization crosslinking reaction. As discussed above latentcrosslinking is can be effected by thermal or photochemical means.

As discussed above, monomers containing trialkoxysilyl groups can becrosslinked by latent crosslinking in the presence of a cationicinitiator agent. A polymerization stable cationic initiator can be canbe thermally activated to induce the latent crosslinking of the silylgroups. Suitable cationic crosslinking initiators include, for example,dibutyltin dilaurate, dimethyltin dilaurate, and dioctyltin dilaurate.

The amount of multifunctional norbornene-type crosslinkable monomers andpost crosslinkable monomers that are optionally present in the reactionmixture can range from about 0.1 mole percent to about 50 mole percentbased on the total monomer in the monomer mixture to be reacted. In oneembodiment, the amount of crosslinking agent ranges from about 1 molepercent to about 25 mole percent of the total monomer mixture. Inanother embodiment,the amount of crosslinking agent ranges from about 1mole percent to about 10 mole percent of the total monomer mixture.

Monomer Polymerization

The monomers of the invention are polymerized in solution or in mass.The catalyst is added to the reaction medium containing the desiredmonomer(s) as a preformed single component catalyst or the catalyst canbe formed in situ by admixing the pro-catalyst component, the Group 15electron donor component, and the WCA salt activator component in thereaction medium. When the pro-catalyst is ligated with the Group 15electron donor component, it is not necessary to employ the Group 15electron donor as a separate component. In one in situ embodiment theligated pro-catalyst component (e.g., containing desired ligandgroup(s)) is admixed with the WCA salt activator component in thereaction medium. In another in situ embodiment a pro-catalyst componentwith or without ligands is admixed with a desired ligand containingcomponent(s) and the WCA salt activator component in the reactionmedium. The pro-catalyst components are generically exemplified in thepreformed catalyst preparation equations (1) to (4) set forth above. Inone embodiment, the molar ratio of pro-catalyst (based on the Group 10metal):Group 15 electron donor component:WCA salt is 1:1-10:1-100. Inanther embodiment, the ratio is 1:1-5:1-20. In yet another embodiment,the ratio is 1:1-2:1-5. In embodiments of the invention where thepro-catalyst is ligated with a Group 15 electron donor ligand and/or alabile neutral electron donor ligand, the molar ratio of pro-catalyst(based on the metal content) to WCA salt is 1:1-100. In anotherembodiment, the ratio is 1:1-20. In yet another embodiment, the ratio is1:1-5. The order of addition of the various catalyst components to thereaction medium is not important.

The polymers prepared by the process of the invention are additionpolymers of polycycloolefinic repeating units linked through2,3-enchainment. The repeating units are polymerized from apolycycloolefin monomer or combination of polycycloolefin monomers thatcontain at least one norbornene-type moiety as described herein.

Solution Process

In the solution process the polymerization reaction can be carried outby adding a solution of the preformed catalyst or individual catalystcomponents to a solution of the cycloolefin monomer or mixtures ofmonomers to be polymerized. The amount of monomer in solvent, in oneembodiment, ranges from 10 to 50 weight percent. In another embodiment,the amount of monomer in solvent ranges from 20 to 30 weight percent.After the single component catalyst or catalyst components are added tothe monomer solution, the reaction medium is agitated (e.g., stirred) toensure complete mixing of catalyst and monomer components.

The polymerization reaction temperatures can range from about 0° C. toabout 150° C. In another embodiment, the polymerization reactiontemperatures can range from about 10° C. to about 100° C. In yet anotherembodiment, the polymerization reaction temperatures can range fromabout 20° C. to about 80° C.

Examples of solvents for the polymerization reaction include but are notlimited to alkane and cycloakane solvents such as pentane, hexane,heptane, and cyclohexane; halogenated alkane solvents such asdichloromethane, chloroform, carbon tetrachloride, ethylchloride,1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane,2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, and 1-chloropentane; aromatic solvents such asbenzene, xylene, toluene, mesitylene, chlorobenzene, anisole ando-dichlorobenzene, Freon® 112 halocarbon solvent, water; or mixturesthereof. In one embodiment, the solvent is selected from cyclohexane,toluene, mesitylene, dichloromethane, 1,2-dichloroethane, and water.

When an aqueous polymerization medium is desired, the Group 15 electrondonor ligand or component may be chosen from the water solublephosphines set forth above, although this is not a strict requirement.The polymerization reaction can be conducted in suspension or emulsion.In suspension, the monomers are suspended in an aqueous mediumcontaining a suspension agent selected from one or more water solublesubstances such as, for example, polyvinyl alcohol, cellulose ether,partially hydrolyzed polyvinyl acetate, or gelatin and then carrying outthe reaction in the presence of the catalyst system of the invention.

The emulsion polymerization can in general be carried out by emulsifyingthe monomers in water or a mixed solvent of water and a water-miscibleorganic solvent (such as methanol, or ethanol). In one embodiment, thisis done in the presence of at least one emulsifying agent. Then, theemulsion polymerization is carried out in the presence of the catalystas discussed herein. Emulsifying agents include, for example, mixed acidsoaps containing fatty and rosin acids, alkyl sulfonate soaps and soapsof oligomeric naphthalene sulfonates.

Mass Process

In the mass polymerization process according to the invention at leastone monomer component (e.g., at least one cycloolefinic monomer) ispolymerized using a catalyst system. In another embodiment, the masspolymerization process according to the invention polymerizes at leastone monomer crosslinking component (e.g., at least one cycloolefiniccrosslinking monomer) using a catalyst system. In yet anotherembodiment, the mass polymerization process according to the inventionis a two component monomer system (i.e. at least two cycloolefinicmonomers of which none, one or two can be a crosslinking monomer) whichis polymerized using a catalyst system. In still another embodiment, themass polymerization process according to the invention is at least athree component monomer system (i.e. at least two cycloolefinic monomersof which at least one of which is a crosslinking monomoer) which ispolymerized using a catalyst system.

The term mass polymerization refers to a polymerization reaction whichis generally carried out in the substantial absence of a solvent. Insome cases, however, a small proportion of solvent is present in thereaction medium. Small amounts of solvent can be conveyed to thereaction medium via the introduction of the catalyst system componentswhich are in some cases dissolved in solvent. Solvents also can beemployed in the reaction medium to reduce the viscosity of the polymerat the termination of the polymerization reaction to facilitate thesubsequent use and processing of the polymer. The amount of solvent thatcan be present in the reaction medium ranges from 0 to about 20 percentbased on the weight of the monomer(s) present in the reaction mixture.In another embodiment, the amount of solvent that can be present in thereaction medium ranges from 0 to about 10 percent based on the weight ofthe monomer(s) present in the reaction mixture. In still anotherembodiment, the amount of solvent present that can be in the reactionmedium ranges from 0 to about 1 percent, based on the weight of themonomer(s) present in the reaction mixture. In one embodiment, thesolvent or solvents utilized are chosen such that the catalyst systemcomponents dissolve therein. Examples of solvents include, but are notlimited to, alkane and cycloalkane solvents such as pentane, hexane,heptane, and cyclohexane; halogenated alkane solvents such asdichloromethane, chloroform, carbon tetrachloride, ethylchloride,1,1-dichloroethane, 1,2-dichloroethane, 1-chloropropane,2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, and 1-chloropentane; esters such asethylacetate, i-amylacetate; ethers such as THF and diethylether;aromatic solvents such as benzene, xylene, toluene, mesitylene,chlorobenzene, anisole and o-dichlorobenzene; and halocarbon solventssuch as Freon® 112; and mixtures thereof. In one embodiment, the solventor solvents is/are selected from benzene, fluorobenzene,o-difluorobenzene, p-difluorobenzene, pentafluorobenzene,hexafluorobenzene, o-dichlorobenzene, chlorobenzene, toluene, o-, m-,and p-xylenes, mesitylene, cyclohexane, ethylacetate, THF, anddichloromethane.

A ligated pro-catalyst containing a Group 15 electron donor ligand isprepared in solvent and then added to the desired monomer or mixture ofmonomers containing the dissolved WCA salt activator. The reactionmixture is mixed and the reaction is permitted to proceed from about 1minute to about 2 hours. The reaction mixture can be optionally heatedat a temperature ranging from about 20° C. to about 200° C. Thepolymerization temperature is not specifically limited. In oneembodiment, the polymerization temperature is in the range of 20° C. to120° C. In another embodiment, the polymerization temperature is in therange of 20° C. to 90° C.

The polymerization reaction can be carried out under an inert atmospheresuch as nitrogen or argon. Advantageously, however, it has been foundthat the catalyst system components of the invention are moisture andoxygen insensitive, allowing for less stringent handling and processingconditions. Following the initial polymerization reaction a polymercement is obtained. The cement can be applied to a desired substrate orconveyed into a mold and post cured to complete the polymerizationreaction.

Without wishing to be bound by theory of invention it is believed thatpost curing is desirable from the standpoint of monomer to polymerconversion. In a mass process the monomer is essentially the diluent forthe catalyst system components. As monomer is converted to polymer aplateau is reached beyond which conversion of monomer to polymer can gono higher (vitrification). This conversion barrier results from the lossof reactant mobility as the reaction medium becomes converted to apolymeric matrix. Consequently, the catalyst system components andunconverted monomer become segregated and can not react. It is wellknown that diffusivity within a polymer decreases dramatically as thepolymer passes from the rubbery state to the glassy state. It isbelieved that post curing at elevated temperatures increases themobility of the reactants in the matrix allowing for the furtherconversion of monomer to polymer.

Post curing of the polymers of the present invention is, in oneembodiment, conducted at elevated temperatures for a time periodsufficient to reach a desired conversion of monomer to polymer. In oneembodiment, the post curing cycle is conducted for about 1 to about 2hours over a temperature range of from about 100° C. to about 300° C. Inanother embodiment, the post curing cycle is conducted for about 5.0 toabout 4 hours at a over a temperature range of from about 100° C. toabout 300° C. In another embodiment, the post curing cycle is conductedfor 1 to 2 hours over a temperature range of from about 125° C. to about200° C. In still another embodiment, the post curing cycle is conductedfor 1 to 2 hours over a temperature range of from about 140° C. to about180° C. The cure cycle can be effected at a constant temperature or thetemperature can be ramped, e.g., incrementally increasing the curingtemperature from a desired minimum curing temperature to a desiredmaximum curing temperature over the desired curing cycle time range. Inone embodiment (A) the temperature ramping can be effected by followinga gradual increasing slope on a temperature vs. time plot from thedesired minimum temperature to the desired maximum temperature in thecure cycle. In this embodiment when the maximum temperature is reached,the temperature maximum can optionally be held for a desired period oftime until the desired cure state is attained. In an alternateembodiment (B) the temperature ramping can follow a stepwise curve on atemperature vs. time plot. In this embodiment the temperature rampingproceeds in step fashion from the desired minimum cure temperature tothe desired maximum cure temperature in the cure cycle. In anotherembodiment (C) the post cure can be effected by combining post cureembodiments (A and B) wherein the cure cycle encompasses a combinationof steps and slopes from the desired minimum cure temperature to thedesired maximum cure temperature. In still another embodiment (D and E)the cure cycle can follow a curve from the desired minimum curetemperature to the desired maximum cure temperature. In embodiments A,B, and C it should be noted that the rise and run of the slope do nothave to be constant between the minimum and maximum cure temperatures ofthe cure cycle. In other words the rise and run can vary when proceedingfrom the desired minimum to desired maximum cure temperatures Theforegoing cure cycle temperature ramping curves are illustrated below.

Ramping of the temperature during the cure cycle is advantageous becauseit diminishes the potential for catalyst degradation and thevolatilization of unconverted monomer.

In another embodiment, the polymerization and the post-curing are bothconducted together. In one embodiment, the polymerization/post-cure isconducted for 1 to 2 hours at a temperature in the range of from about20° C. to about 200° C. In another embodiment, the polymerization/postcure is conducted for 1 to 2 hours at a temperature in the range of fromabout 125° C. to about 200° C. In still another embodiment, the postcuring cycle is conducted for 1 to 2 hours over a temperature range offrom about 140° C. to about 180° C.

Alternatively, the polymerization/post-cure can be conducted at morethan one temperature (i.e. within a range of temperatures). For example,the polymerization/post-cure can be conducted over a range oftemperatures similar to the ranges given immediately above. If thepolymerization/post-cure is being conducted within a range oftemperatures, the temperature at which the polymerization/post-cure isbeing conducted can be altered according to the discussion had abovewith regard to temperature ramping.

Optionally, additives may include, but are not limited to, thoseselected from pigments, dyes, non-linear optical dyes, erbium complexes,praseodymium complexes, neodymium complexes, plasticizers, lubricants,flame retardants, tackifiers, antioxidants (e.g., Irganox® 1010, 1076,3114, or Cyanox® 1790), UV stabilizers, masking agents, odor absorbingagents, crosslinking agents, synergists (e.g., Irgafos® 168,thiodipropionic acid dilauryl ester, or a combination of both),tougheners and impact modifiers, polymeric modifiers and viscosifiersand mixtures thereof (e.g., poly-iso-butylene, EPDM rubbers, siloxaneoligomers and mixtures thereof), can be added by mixing one or more ofthem into the monomer medium before the polymerization reaction isinitiated. The identity and relative amounts of such components are wellknown to those skilled in the art and need not be discussed in detailhere.

The optional additives are employed to enhance the processing,appearance and/or the physical properties of the polymer. For example,the additives can be utilized to enhance and modify inter alia thecoefficient of thermal expansion, stiffness, impact strength, dielectricconstant, solvent resistance, color, optical properties and odor of thepolymer product. The viscosifiers are employed to modify the viscosityand shrinkage of the monomeric mixture before the polymerizationreaction is initiated. Suitable viscosity modifiers include elastomersand the norbornene-type polymers of the present invention. The viscositymodifiers can be dissolved in the polymerizable monomers of theinvention to increase the viscosity of the monomer reaction mixture. Asdiscussed above, crosslinking can be effected during the initialpolymerization reaction of the monomer mixture or during a postpolymerization thermal or photochemical curing step.

In one embodiment, when a pro-catalyst is employed in the masspolymerization system of the invention, the molar ratio of monomer topro-catalyst (based on metal content) to WCA salt activator ratiosranges from about 500,000:1:1 to about 5,000:1:20. In anotherembodiment, the molar ratio of monomer to pro-catalyst (based on metalcontent) to WCA salt activator ratios ranges from about 250,000:1:5 toabout 20,000:1:10. In yet another embodiment, the molar ratio of monomerto pro-catalyst (based on metal content) to WCA salt activator ratiosranges from about 200,000:1:20 to about 100,000:1:1.

Further information regarding the above can be found in InternationalPatent Application Publication No. WO 00/20472 to The BF GoodrichCompany, published on Apr. 13, 2000, and International PatentApplication Publication No. WO 00/34344 also to The BF Goodrich Company,published on Jun. 15, 2000, both of which are hereby incorporated hereinby reference in their entireties.

Optical Waveguide Formulations

In one embodiment, the polymer compositions for use in the presentinvention have from about 100 to about 100,000 repeating units asdefined above by one or more of Structures VII, VIIa and VIIb. Inanother embodiment, the polymer compositions for use in the presentinvention have from about 500 to about 50,000 repeating units as definedabove by one or more of Structures VII, VIIa and VIIb. In yet anotherembodiment, the polymer compositions for use in the present inventionhave from about 1,000 to about 10,000 repeating units as defined aboveby one or more of Structures VII, VIIa and VIIb.

In one embodiment, a waveguide is formed using one of the methodsdisclosed below with at least two polyacrylate, polyimide,benzocyclobutene, cyclic olefin polymers, such that the core materialand the clad material have a difference in their indices of refractionat 830 nm (Δn at 830 nm), core versus clad, of at least 0.00075 or more(or at least 0.05% when the clad refractive index is 1.5). That is, therefractive index of the polymer core layer is at least 0.05% greaterthan the refractive index of the at least one polymer cladding layer. Ifthe waveguide is a three layer waveguide, the cladding layers (topcladding layer and sub-cladding layer) may be different polymers layersso long as both cladding layers have a refractive index which is atleast 0.05% less than that of the polymer used to form the core layer.

In another embodiment, when the waveguide is to be formed from cyclicolefin monomers, both the core and cladding polymer layers of theoptical waveguide of the present invention are formulated to include atleast one cyclic olefin monomer (e.g., at least one norbornene-typemonomers) and/or at least one crosslinking monomer, at least onepro-catalyst (see the discussion of pro-catalysts above under theCatalyst Preparation heading), at least one co-catalyst (i.e., a WCAsalt having a weakly coordinating ion, see above), and optionally one ormore of the additives discussed above (see the discussion under the MassProcess heading).

Such a mixture is polymerized using the above-described masspolymerization process (see the discussion under the Mass Processheading) by either adding the pro-catalyst to a mixture containing theat least one cyclic olefin monomer, the co-catalyst, and any optionaladditives, or by adding the co-catalyst to a mixture containing the atleast one cyclic olefin monomer, the pro-catalyst, and any optionaladditives. In both these situations the active catalyst is generated insitu.

In yet another embodiment, each of the clad and core formulations (whichdiffer to the extent necessary to produce the required difference intheir respective refractive indices) is formed from a 2-componentsystem. That is, the clad formulation is produced from at least twocomponents, Components A and B. On is the other hand, the coreformulation is also produced from at least two components, Components Cand D. Each of components A through D contain at least onenorbornene-type monomer.

In another embodiment, Components A and B are two substantiallyidentical mixtures of the at least one norbornene-type monomer and/or atleast one crosslinking monomer. The difference between Components A andB generally arises from the inclusion of a pro-catalyst in Component Aversus the inclusion of a co-catalyst in Component B. Additionaldifferences between Component A and Component B may exist. For example,Component A may contain an optional additive not present in Component B,or vice versa.

In one embodiment, Component A comprises at least one norbornene-typemonomer and/or at least one crosslinking monomer, at least onepro-catalyst and optionally an additive as discussed above (such as anantioxidant). Whereas, Component B comprises the same norbornene-typemonomer(s), the same crosslinking agent(s), at least one co-catalyst,and optionally an additive (such as an antioxidant) and/or a synergist.In this situation, polymerization is conducted using the Mass Processpolymerization method by mixing equal amounts of Components A and B,thereby generating the active polymerization catalyst in situ.

Alternatively, each of the clad and/or clad formulations may be a onepart mixture in which at least one norbornene-type monomer and/or atleast one crosslinking monomer, at least one co-catalyst, and anyoptional additives are present. To cause the polymerization reaction tooccur a pro-catalyst is added to the above mixture(s). In anotherembodiment, each of the core and/or clad formulations may be a one partmixture in which at least one norbornene-type monomer and/or at leastone crosslinking agent, at least one pro-catalyst, and any optionaladditives are present. To cause the polymerization reaction to occur aco-catalyst is added to the above mixture(s). Again it is noted, thatgenerally the clad and core formulations differ with respect to the atleast one norbornene-type monomer and/or at least one crosslinkingmonomer present therein. It is this difference, in one embodiment, thatpermits the formation of polymers having the necessary difference intheir respective refractive indices.

In another embodiment, each of the clad and/or core formulations containat least one norbornene-type crosslinking monomer (as discussed above),at least one co-catalyst and any optional additives as discussed above.To cause the polymerization reaction to occur a pro-catalyst is added tothe above mixture(s). Alternatively, the above mixture could be dividedinto two or more portions and the co-catalyst added to one portion whilethe pro-catalyst is added to another portion. In this instance,polymerization is accomplished by the combination of all of theportions.

In yet another embodiment, each of the core and/or clad formulation maybe a one part mixture in which at least one norbornene-type crosslinkingmonomer, at least one pro-catalyst, and any optional additives arepresent. To cause the polymerization reaction to occur a co-catalyst isadded to the above mixture(s). Again it is noted, that generally theclad and core formulations differ with respect to the at least onenorbornene-type crosslinking monomer present therein. It is thisdifference, in one embodiment, that permits the formation of polymershaving the necessary difference in their respective refractive indices.Alternatively, the above mixture could be divided into two or moreportions and the co-catalyst added to one portion while the pro-catalystis added to another portion. In this instance, polymerization isaccomplished by the combination of all of the portions.

Below are some exemplary clad and core formulations. It should be notedthat these formations are exemplary in nature and are not meant to serveas an exhaustive list of the possible formulations for each of the cladand core. Rather, other clad and core formulations can be produced inview of the above disclosure so long as the refractive index of thepolymer produced using the core formulation is at least 0.05% largerthan that of the polymer produced using the clad formulation.

Exemplary Clad Formulations

In one embodiment, the clad formulation contains: (1) onenorbornene-type monomer containing a pendant C₄ to C₂₀ alkyl group, (2)one norbornene-type monomer containing a pendant C₁ to C₁₀ alkoxysilylgroup, and (3) at least one crosslinking agent (as disclosed above). Inaddition to components (1), (2) and (3), the clad formulation alsocontains at least one pro-catalyst, at least one co-catalyst, andoptionally an additive or additives as discussed above. As noted above,if components (1), (2) and (3) are all present in one mixture theneither the pro-catalyst or the co-catalyst is held out of the mixtureand added to the mixture at a later time.

Alternatively, components (1), (2) and (3) can be divided into two ormore portions and the pro-catalyst added to one portion to formComponent A (which can optionally include an additive or additives). Toanother portion of components (1), (2) and (3) is added the co-catalystto form Component B (which can optionally include the same, different oradditional additives as Component A). Polymerization is accomplished inthis embodiment by combining Component A and Component B (along with anyother portion of component (1), (2) and (3) not used to for Components Aand B).

In one embodiment, component (3) is at least one crosslinking agentselected from dimethyl bis(norbornenemethoxy) silane, octamethyl1,8-bis(norbornenemethoxy) tetrasiloxane, bis(norbornenemethyl)acetal ora fluorinated crosslinking agent (such as F-Crosslinking Agents I and IIshown above).

Exemplary Core Formulations

In one embodiment, the core formulation contains: (1) onenorbornene-type monomer containing a pendant C₄ to C₂₀ alkyl group, (2)one norbornene-type monomer containing a pendant silane group with atleast one C₆ to C₁₂ aryl group attached to the Si atom of the silanegroup, and (3) at least one crosslinking agent (as disclosed above). Inaddition to components (1), (2), and (3) the core formulation alsocontains at least one pro-catalyst, at least one co-catalyst, andoptionally an antioxidant and/or a synergist. If components (1), (2) and(3) are all present in one mixture than either the pro-catalyst or theco-catalyst is held out of the mixture and added to the mixture at alater time.

Alternatively, components (1), (2) and (3) can be divided into two ormore portions and the pro-catalyst added to one portion to formComponent A (which can optionally include an additive such anantioxidant). The other portion of components (1), (2) and (3) can becombined with the co-catalyst to form Component B (which can optionallyinclude an additive such as an antioxidant and/or a synergist).

In one embodiment, component (3) is at least one crosslinking agentselected from dimethyl bis(norbornenemethoxy) silane, octamethyl1,8-bis(norbornenemethoxy) tetrasiloxane, bis(norbornenemethyl)acetal ora fluorinated crosslinking agent (such as F-Crosslinking Agents I and IIshown above).

In one embodiment, the molar ratio, stated in mole percent, of component(1):component (2):component (3) in either the clad or core formulationis 60-90:5-20:5-20. In another embodiment, the molar percent ratio ofcomponent (1):component (2):component (3) is 65-85:7.5-20:7.5-17.5. Instill another embodiment, the molar ratio of component (1):component(2):component (3) is 75-85:10-20:5-15.

Examples of Crosslinking Agents; and Clad and Core Formulations

The following examples are detailed descriptions of methods ofpreparation and use of certain compositions of the present invention.The detailed preparation descriptions fall within the scope of, andserve to exemplify, the more generally described compositions andformulations set forth above.

Additionally, in the examples below Lithium tetrakis (pentafluoro phenylborate)·2.5 etherate is sometimes referred to in shorthand as LiFABA(see for example Table 2), and(allyl)palladium(tricyclohexylphosphine)trifluoroacetate is referred toas Allyl Pd—PCy₃TFA.

X. Examples of Formation of Selected Crosslinking Agents

(X1) Synthesis of Dimethyl bis(Norbornenemethoxy)silane

Norbornene methanol (108.5 g, 0.87 mol.) is added dropwise tobis(dimethylamino) dimethyl silane (63.97 g, 0.43 mol.) in a reactorwhich is connected to a scrubber containing dilute hydrochloric acid.The reaction mixture is stirred for about 4 hours. The mixture is thenconnected to a vacuum, and residual amounts of the amine are removed.Pure product is obtained by distillation under vacuum (117 g, ˜90%yield).

The above reaction is also carried out using the dimethyl dichlorosilane instead of bis(dimethylamino) dimethyl silane.

To a vigorously stirred mixture of 5-norbornene methanol (50 g, 0.40mol.), triethyl amine (49 g, 0.49 mol.) and toluene (400 mL), dimethyldichlorosilane (25.8 g, 0.20 mol.) is added dropwise. Stirring at roomtemperature results in the formation of salts. The crude product isisolated by filtration of the salts, washing the toluene solution withwater (3 times) followed by evaporation of toluene. Distillation isconducted under vacuum to obtain pure product (53 g, ˜87% yield).

(X2) Synthesis of Octamethyl 1,8-bis(Norbornenemethoxy) Tetrasiloxane:

Norbornenemethanol (21.2 g, 0.17 mol.) is added dropwise to a solutionconsisting of octamethyl dichlorotetrasiloxane (30 g, 0.085 mol.),triethyl amine (21 g, 0.21 mol.) and toluene (300 mL). The reactionmixture is stirred for 8 hours at room temperature. The solids that areformed (triethylamine hydrochloride) are filtered off. The toluenesolution is then washed 3 times with small amounts of distilled waterand the crude product is obtained by removing the toluene. Pure productis obtained by distillation under vacuum (39 g, ˜87% yield).

(X3) Synthesis of bis(Norbornenemethyl)acetal

A mixture of norbornenemethanol (100 g, 0.81 mol.), formaldehyde (˜37%)(32.6 g, 0.40 mol.) and a catalytic amount of p-toluene sulfonic acid(0.2 g) are heated at 100° C. in a flask which is directly connected toa Dean Stark Trap. As the reaction proceeds, the amount of water in thetrap increases. Within about 3 hours, the reaction is complete. Pureproduct is obtained by distilling under vacuum (72.8 g, ˜70% yield).

Examples of Clad Formulations (One Component)

CL1: Cladding Formulation using Octamethyl1,8-bis(Norbornenemethoxy)tetrasiloxane:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0200 g,2.3×10⁻⁵ mol.) is dissolved in a mixture of monomers consisting ofhexylnorbornene (10 g, 0.056 mol.) octamethyl1,8-bis(norbornenemethoxy)tetrasiloxane (3.9 g, 8.6 mmol.) andtriethoxysilylnorbornene (2.9 g, 0.01 mol.). To the mixture is added0.17 g of Irganox® 1076 (1% by weight).

To this mixture, is added 0.16 mL of catalyst stock solution (3.02×10⁻⁶mol.). (Note: the stock solution was made up by dissolving 0.01 g ofAllyl Pd—PCy₃TFA in 1 mL of dry dichloromethane.)

Cure/post-cure is conducted according to the following schedule: 10 min.at 65° C. and 60 min. at 160° C. After curing the monomer mixture, aclear and good optical quality film is obtained.

CL2: Cladding Formulation using bis(Norbornenemethyl)acetal:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0042 g,4.8×10⁻⁶ mol.) is dissolved in a mixture of monomers consisting ofhexylnorbonene (5 g, 0.028 mol.), bis(norbornenemethyl)acetal (1.57, 6.1mmol.) and triethoxysilylnorbornene (1.54, 6.1 mmol.). To this mixtureis added 0.08 g of Irganox® 1076 (1% by weight).

To this mixture, added 0.08 mL of catalyst stock solution (1.6×10⁻⁶mol.). (Note: the stock solution was made up by dissolving 0.01 g ofAllyl Pd—PCy₃TFA in 1 mL of dry dichloromethane.)

Cure/post-cure is conducted according to the following schedule: 10 min.at 65° C. and 60 min. at 160° C. After curing the monomer mixture, aclear and good optical quality film is obtained.

CL3: Cladding Formulation using F-Crosslinking Agent I:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0061 g,6.9×10⁻⁶ mol.) is dissolved in a mixture of monomers consisting of hexylnorbonene (6.2 g, 0.035 mol), F-Crosslinking Agent I (3.2 g, 4.3 mmol.)and triethoxysilylnorbornene (1.11 g, 4.3 mmol.). To the mixture isadded 0.10 g of Irganox® 1076 (1% by weight).

To this mixture, added 0.1 mL of catalyst stock solution (1.7×10⁻⁶mol.). (Note: the stock solution was made up by dissolving 0.01 g ofAllyl Pd—PCy₃TFA in 1 mL of dry dichloromethane.)

Cure/post-cure is conducted according to the following schedule: 10 min.at 65° C. and 60 min. at 160° C. After curing the monomer mixture, aclear and good optical quality film is obtained.

CL4: Cladding Formulation using F-Crosslinking Agent II:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0061 g,6.9×10⁻⁶ mol.) is dissolved in a mixture of monomers consisting of hexylnorbonene (6.2 g, 0.035 mol), F-Crosslinking Agent II (3.6 g, 4.3 mmol.)and triethoxysilylnorbornene (1.11 g, 4.3 mmol.). To this mixture isadded 0.10 g of Irganox® 1076 (1% by weight).

To this mixture, added 0.1 mL of catalyst stock solution (1.7×10⁻⁶mol.). (Note: the stock solution was made up by dissolving 0.01 g ofAllyl Pd—PCy₃TFA in 1 mL of dry dichloromethane.)

Cure/post-cure is conducted according to the following schedule: 10 min.at 65° C. and 60 min. at 160° C. After curing the monomer mixture, aclear and good optical quality film is obtained.

Example of Clad Formulation (Two Component) CL5

All monomers are degassed using dry nitrogen gas prior to use.

Component A:

To a mixture of hexyl norbornene (33 g, 0.185 mol.), triethoxysilylnorbornene (9.5 g, 0.037 mol.) and dimethyl bis(norbornene methoxy)silane (7.5 g, 0.0247 mol.) is added Allyl Pd—PCy₃TFA (0.0107 g,1.98×10⁻⁵ mol.) dissolved in 0.2 ml of dichloromethane. To this mixtureis added 0.50 g of Irganox® 1076.

Component B:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0689 g,7.91×10⁻⁵ mol.) is dissolved in a mixture of triethoxysilyl norbornene(9.5 g, 0.037 mol.) and dimethyl bis(norbornene methoxy) silane (7.5 g,0.0247 mol.). Once the solids are completely dissolved, hexyl norbornene(33 g, 0.185 mol.) is added to the mixture. Also added to the mixture,and dissolved therein, is Irganox® 1076 (0.50 g). In addition to theantioxidant, 0.25 g of Irgafos® 168 is added as a synergist.

Equal amounts of Components A and B are mixed together and are cured.Cure/post-cure is conduced according to the following schedule: 10 min.at 65° C. and 60 min. at 160° C. After curing the monomer mixture, aclear and good optical quality film is obtained.

The formulation of this example is shown in Table 2 below.

TABLE 2 Total Moles Component B in A Compound Component (A) (g) (g) andB Hexyl Norbornene 33 33 0.3708 Triethoxysilyl 9.5 9.5 0.0742 NorborneneDimethyl 7.5 7.5 0.0493 Bis(Norbornene Methoxy) Silane Total Moles N/AN/A 0.4943 LiFABA N/A 0.0689 7.91 × 10⁻⁵ Ally Pd—PCy₃TFA 0.0107 N/A 1.98× 10⁻⁵ Irganox ® 1076 0.50 0.50 Irgafos ® 168 N/A 0.25

CO1. Example of Core Formulations (Two Component)

All monomers are degassed using dry nitrogen gas prior to use.

Component A:

To a mixture of hexyl norbornene (31.5 g, 0.18 mol.), diphenyl methylnorbornene methoxy silane (11.3 g, 0.035 mol.) and dimethylbis(norbornene methoxy) silane (7.5 g, 0.025 mol.), is added AllylPd—PCy₃TFA (0.0102 g, 1.89×10⁻⁵ mol.) dissolved in 0.2 ml ofdichloromethane. To this mixture is added 0.50 g of Irganox® 1076.

Component B:

Lithium tetrakis (pentafluoro phenyl borate)·2.5 etherate (0.0658 g,7.55×10⁻⁵ mol.) is dissolved in a mixture of diphenyl methyl (norbornenemethoxy) silane (11.3 g, 0.035 mol.) and dimethyl bis(norbornenemethoxy) silane (7.5 g, 0.0247 mol.) and hexyl norbornene (31.5 g, 0.18mol.). To this mixture is added, and dissolved therein, Irganox® 1076(0.50 g). In addition to the antioxidant, 0.25 g of Irgafos® 168 isadded as a synergist.

Equal amounts of Components A and B are mixed together and are cured.Cure/posture is conduced according to the following schedule: 10 min. at65° C. and 60 min. at 160° C. After curing the monomer mixture, a clearand good optical quality film is obtained.

The formulation of this example is shown in Table 3 below.

TABLE 3 Component (A) Component (B) Total Moles Compound (g) (g) in Aand B Hexyl 31.5 31.5 0.3539 Norbomene Diphenyl Methyl 11.3 11.3 0.0706(Norbornene Methoxy) Silane Dimethyl 7.2 7.2 0.0474 Bis(NorbomeneMethoxy) Silane Total Moles N/A N/A 0.4719 LiFABA N/A 0.0658 7.55 × 10⁻⁵Ally Pd-PCy₃ 0.0102 N/A 1.89 × 10⁻⁵ TFA Irganox ® 1076 0.50 0.50Irgafos ® 168 N/A 0.25

Methods of Curing Cyclic Olefin Monomer Formulations and ProducingWaveguides

Cure/Post-Cure:

As discussed above under the Mass Process heading, the monomerformulations of the present invention are polymerized at a temperatureof about 20° C. to about 200° C. for about 1 minute to about 2 hours. Inanother embodiment, the polymerization occurs at a temperature of about20° C. to about 120° C. for about 1 to about 40 minutes. In yet anotherembodiment, polymerization occurs at a temperature of about 40° C. toabout 80° C. for about 5 minutes to about 20 minutes. As noted above,the polymerization reaction can be carried out under an inert atmospheresuch as nitrogen or argon. In another embodiment, the polymerization canbe carried out in a forced air, vented oven.

After polymerization, the polymer may be subjected to a post curingstep. In one embodiment, the post curing step is conducted for about 1to about 2 hours at a temperature range of from about 100° C. to about300° C. (as noted above the temperature during post-cure can beincreased over time). Additionally, in another embodiment, post-cure canbe conducted for about 0.5 to about 4 hours at a temperature in therange of from about 100° C. to about 300° C. In another embodiment, thepost curing step is conducted for about 1 to about 2 hours over atemperature range (or at a temperature in the range) of from about 125°C. to about 200° C. In still another embodiment, the post curing step isconducted for about 1 to about 2 hours over a temperature range of (orat a temperature in the range) from about 140° C. to about 180° C.

Partial Cure/Cure/Post Cure:

In another embodiment, at least one monomer formulation (e.g., either acore composition or a cladding (or clad) composition) is partiallypolymerized (cured) to gel point at a temperature of about 20° C. toabout 120° C. for about 0.1 to about 10 minutes. In another embodiment,the polymerization occurs at a temperature of about 40° C. to about 100°C. for about 1 to about 8 minutes. In yet another embodiment,polymerization occurs at a temperature of about 50° C. to about 70° C.for about 2 minutes to about 6 minutes. As noted above, thepolymerization reaction can be carried out under an inert atmospheresuch as nitrogen or argon. In another embodiment, the polymerization canbe carried out in a forced air, vented oven.

After partial cure, at least one more monomer formulation (not cured)can be placed over or on top of the partially cured monomerformulation(s). In one embodiment, if at least one core composition issubjected to partial cure, then at least one clad composition is placedover the at least one core composition. In another embodiment, if atleast one clad composition is subjected to partial cure, then at leastone core composition is placed over the at least one core composition.In yet another embodiment, the at least one monomer formulation which isplaced over the at least one partially cured monomer formulation can beanother similar formulation (i.e., at least one additional coreformulation over the at least one partially cured core formulation,etc.).

After the desired combination of monomer formulations is present (atleast one of which is partially cured in accordance with the abovediscussion) the combination is cured at a temperature of about 20° C. toabout 200° C. for about 1 minute to about 2 hours. In anotherembodiment, the polymerization occurs at a temperature of about 20° C.to about 120° C. for about 1 to about 40 minutes. In yet anotherembodiment, polymerization occurs at a temperature of about 40° C. toabout 80° C. for about 5 minutes to about 20 minutes. As noted above,the polymerization reaction can be carried out under an inert atmospheresuch as nitrogen or argon. In another embodiment, the polymerization canbe carried out in a forced air, vented oven.

After the combination of monomers has been cured (polymerized), thepolymer combination may be subjected to a post curing step. In oneembodiment, the post curing step is conducted for about 1 to about 2hours at a temperature range of from about 100° C. to about 300° C. (asnoted above the temperature during post-cure can be increased overtime). Additionally, in another embodiment, post-cure can be conductedfor about 0.5 to about 4 hours at a temperature in the range of fromabout 100° C. to about 300° C. In another embodiment, the post curingstep is conducted for about 1 to about 2 hours over a temperature range(or at a temperature in the range) of from about 125° C. to about 200°C. In still another embodiment, the post curing step is conducted forabout 1 to about 2 hours over a temperature range of (or at atemperature in the range) from about 140° C. to about 180° C.

Method of Making Waveguides:

Clad First:

Conventional molding processes of fabrication of waveguides are done ina clad-first fashion. For example, shown in FIG. 1 is a generic processof making a waveguide 1. First at (a) a cladding film 12 (sub-cladding)is formed by casting against a master 10 (a nickel master or othersuitable master) in a molding process such as injection molding, hotembossing and reactive casting (see (a) of FIG. 1) and subsequentingsubjected to curing. The sub-cladding layer 12 is removed from themaster 10 (see (b) of FIG. 1) and a liquid core material 14 is thenapplied onto the featured side of the sub-cladding film 12 and forcedinto the grooves by pressure using, for example, a Doctor blade 16 (see(c) of FIG. 1). Thereafter, the liquid core material 14 is cured to forma ribbed waveguide structure 14 a (see (d) of FIG. 1). It should benoted that the waveguide structure depicted in FIG. 1 is ribbed.However, any suitable waveguide structure can be formed (e.g., a web,lattice, matrix, buried channels, etc.). Next, a top cladding layer 18is formed over a portion or all of the waveguide structure 14 a by adepositing thereupon a liquid clad material which upon curing forms thetop cladding layer 18 (see (e) of FIG. 1).

Alternatively, the top cladding layer 18 may be formed independentlyrather than being polymerized from a liquid formulation placed on top ofthe waveguide structure 14 a, and optionally a portion of thesub-cladding layer 12. In such an embodiment, the top cladding layer 18may be joined to the exposed portion of the waveguide structure 14 ausing a suitable adhesive attachment means (e.g., a layer of liquidcladding material which acts as a glue).

In yet another embodiment, the method of FIG. 1 can be halted after step(d) has been completed. In such a case, a two layer waveguide isobtained rather than the three layer wave guide discussed above.

Using one of the above clad-first approaches results in the productionof two and three layer waveguides. Additionally, this conventionalclad-first approach can yield a variety of waveguide structures such asan array of buried rib waveguides, as shown in FIGS. 2A to 2C. A carefulbalance of the dimensions (height, width, spacing, and thickness of theslab region) of the rib guides, along with control over the differencein the refractive index between the core and clad layers, and theoperating wavelength can lead to a waveguide structure in which light iswell confined (FIGS. 2B and 2C).

It should be noted that core/clad compositions disclosed herein can beused in other prior art waveguide formation methods (e.g.,micro-molding/embossing; reactive ion etching; UV laser and e-beamwriting; photochemical delineation; photo-bleaching; induced dopantdiffusion (photo-induced dopant diffusion, photolocking and selectivepolymerization); selective poling of electro-optically active moleculesinduced by an electric field; and polymerization of self-assembledprepolymers.

Additionally, the master used in this embodiment may have a waveguidestructure whose channels are actually bigger than desired in the finalproduct. Such features permit a non-stick coating (e.g., PTFE) or amold-release agent to be applied over the master so as to facilitateremoval of the sub-cladding layer 12 from the master 10. Alternatively,separation of the sub-cladding layer from the master may be facilitatedby running cold water over the sub-cladding layer.

Core-First Method:

Using the core-first method discussed below, a waveguide, even anisolated buried channel wave guide, can be formulated. For the purposesof this discussion, the method will be discussed in relation to anisolated buried channel waveguide. However, it is within the scope ofthis invention to form other waveguide structures (such as a ribbedstructure).

Compared with the conventional clad-first approach, the fabricationsteps in the core-first approach are executed in reverse order, as shownin FIG. 3. The general process is described as follows. A mixture of acore material 30 is poured onto the surface of a master 32 (e.g., Ni, Simasters, etc.) having grooves 34 formed in the shape and dimensions ofthe desired waveguide pre-structure (see (a) and (b)). For example, foran isolated buried channel waveguide structure the channels are fromabout 1 μm to about 200 μm in width and from about 1 μm to about 200 μmin height. However, any desired thickness and height may be obtained solong as the channels are neither too narrow or too shallow to accept thecore material.

A Doctor blade 36 is set to rest directly on the surface of the master(where a buried structure is desired) and used to scrape away the excessliquid core mixture 30 (see (b) of FIG. 3). Next, the core material 30left in the grooves is cured to form at least one waveguide structure 30a. If the core material 30 is one of the core materials described above,the core material 30 can be cured in accordance with any one of theabove-mentioned methods.

After the core material 30 left in the grooves is fully cured, asdescribed above (see (c) of FIG. 3), a mixture of a cladding material 38is poured onto the top of the core containing master so as to cover theat least one exposed surface of the waveguide structure(s) 30 a. Thethickness of the sub-cladding layer is also controlled by a Doctor blade36 (see (d) of FIG. 3). Upon curing under the proper conditions, asub-clad layer 40 is formed which is in contact with at least onesurface of the waveguide structure(s) (see (e) of FIG. 3). Next, thesub-clad layer 40/waveguide structure(s) 30 a combination is removedfrom the master 32 and flipped over so that the sub-lad layer is on thebottom (see (f) of FIG. 3).

In one embodiment, the thickness of sub-clad layer is sufficient toallow for the removal of the sub-clad layer 40 and the waveguidestructure(s) 30 a from the master 32 without causing damage thereto. Inanother embodiment, the thickness of the each clad (sub-clad and topclad) is from about 2 μm to about 20,000 μm or are in total about 4 μmto about 20,000 μm. In yet another embodiment, the thickness of eachclad layer is about 10 μm to about 10,000 μm, or are in total about 20μm to about 10,000 μm. It should be noted that the height of thetop-clad by definition includes the height of the core layer (see (h) ofFIG. 3).

Next, a top cladding material 42 is applied to the core side of the filmand the thickness thereof is also controlled by a Doctor blade 36 (see(g) of FIG. 3). Thereafter, the top cladding material 42 is cured toform a top cladding layer 42 a. Upon completion of the curing process ofthe top cladding layer a waveguide 50 is formed (see (h) of FIG. 3). Itshould be noted, that curing of this third layer results in athree-layer polymer film containing isolated channel waveguide core 30 aburied between the sub-cladding layer 40 and the top cladding layer 42a.

Alternatively, if a two layer optical waveguide is desired the aboveprocess is halted after step (f) is complete.

Additionally, the master used in this embodiment may have a corestructure(s) which are actually bigger than desired in the finalproduct. Such features permit a non-stick coating (e.g., PTFE) or amold-release agent to be applied over the master to help facilitate theremoval of the core structures 30 a and the sub-cladding layer 40 fromthe master 32. Alternatively, separation of the sub-cladding layer fromthe master is facilitated by running cold water over the sub-claddinglayer.

Compared with the clad-first approach, this core-first approach makesthe core structures of waveguides by casting on a master (e.g., Ni orSi) that has no interaction with the liquid core precursor. Thismodification in the fabrication process permits the complete removal ofthe slab region of the core layer and also enables an easy filling offine channels by using a low-viscosity core prepolymer mixture, whichsimplifies the production of isolated, buried channel waveguides.

Optical micrographs of samples of two-layer and three-layer waveguidestructures made using the core-first method are shown in FIGS. 4A to 4Dand, in one embodiment, the previously discussed cyclic olefincompositions (e.g., using the core and clad formulations discussedabove). The waveguides of FIGS. 4A to 4D were produced using the cladcomposition detailed in Table 2 above, and the core composition detailedin Table 3 above. FIG. 4A shows a two-layer isolated channel waveguidestructure; FIG. 4B shows a three-layer buried channel waveguidestructure; FIG. 4C is a schematic diagram of the end view of thewaveguide array of FIG. 4B (dimensions 13 μm wide, 16 μm tall, spaced by13 μm) with the position of an input optical fiber shown as a shadedcircle; and FIG. 4D is a photograph of the waveguide output when lightfrom a diode laser (λ=820 nm) is coupled into a single core structure 30a as shown in FIG. 4C. The output pattern shows that the guide ismultimode at 820 nm and there is no cross coupling between adjacentguides.

The core-first method is also applicable to any other suitable polymersystem which include, but are not limited to, polyacrylates (such asdeuterated polyfluoromethacrylate), polyimides (such as cross-linkedpolyimides or fluorinated polyimides), or benzocyclobutene.

With regard to FIGS. 5A and 5B, these figures depict the conditioncalled “swelling”. “Swelling” may occur during a clad-first approach forforming waveguides (see FIG. 1). Although not wishing to be bound to anyone theory, it is believed that swelling occurs during thepolymerization of the core composition in the previously polymerizedsub-cladding structure. In some instances “swelling” may be undesirable.Thus, using, for example, the above-mentioned core-first approach towaveguide formation (see FIG. 3) it is possible to reduce and/oreliminate such “swelling”. This is shown by comparing FIG. 5A (formedusing the above-mentioned clad-first approach) to that of FIG. 5B(formed using the above-mentioned core-first approach).

Modified Core-First Method:

In another embodiment, the above-mentioned core first method can bemodified to take advantage of the previously discussed partialcure/cure/postcure polymerization method (see above). For the purposesof this discussion, the method will be discussed in relation to anisolated buried channel waveguide. However, it is within the scope ofthis invention to form other waveguide structures (such as a ribbedstructure).

This modified core first method will be discussed with reference toFIGS. 6, 7A and 7B. Referring to FIG. 6, the general modified core firstprocess is described as follows. A mixture of a core material 60 ispoured onto the surface of a master 62 (e.g., Ni, Si masters, etc.)having grooves 64 formed in the shape and dimensions of the desiredwaveguide structure (see (a) and (b)). For example, for an isolatedburied channel waveguide structure the channels are from about 1 μm toabout 200 μm in width and from about 1 μm to about 200 μm in height.However, any desired thickness and height may be obtained so long as thechannels are neither too narrow or too shallow to accept the corematerial.

A Doctor blade 66 is set to rest directly on the surface of the master(where a buried structure is desired) and used to scrape away the excessliquid core mixture 60 (see (b) of FIG. 6). Next, the core material 60left in the grooves is partially cured to form at least onepre-waveguide structure 60 a. If the core material 60 is one of the corematerials described above, the core material 60 is partially cured inaccordance with the above-mentioned partial cure/cure/post cure method.

After the core material 60 left in the grooves is partially cured, asdescribed above (see (c) of FIG. 6), a mixture of a cladding material 68is poured onto the top of the core containing master so as to cover theat least one exposed surface of the waveguide structure(s) 60 a. Thethickness of the sub-cladding layer is also controlled by a Doctor blade66 (see (d) of FIG. 6). Upon curing under the proper conditions (see thediscussion under partial cure/cure/post cure above), a sub-clad film 70is formed which is in contact with at least one surface of the waveguidestructure(s) (see (e) of FIG. 6). Next, the sub-clad layer 70/waveguidestructure(s) 60 a combination is removed from the master 62 and flippedover so that the sub-clad layer is on the bottom (see (f) of FIG. 6).

In one embodiment, the thickness of sub-clad layer is sufficient toallow for the removal of the sub-clad layer 70 and the waveguidestructure(s) 60 a from the master 62 without causing damage thereto. Inanother embodiment, the thickness of the each clad (sub-clad and topclad) is from about 2 μm to about 20,000 μm or are in total 4 μm toabout 20,000 μm. In yet another embodiment, the thickness of each cladlayer is about 10 μm to about 10,000 μm, or are in total about 20 μm toabout 10,000 μm. It should be noted that the height of the top-clad bydefinition includes the height of the core layer (see (h) of FIG. 6).

Next, a top cladding material 72 is applied to the core side of the filmand the thickness thereof is also controlled by a Doctor blade 66 (see(g) of FIG. 6). Thereafter, the top cladding material 72 is cured toform a top cladding layer 72 a. Upon completion of the curing process ofthe top cladding layer a waveguide 75 is formed (see (h) of FIG. 6). Itshould be noted, that curing of this third layer results in athree-layer polymer film containing isolated channel waveguide core 60 aburied between the sub-cladding layer 70 and the top cladding layer 72a.

Alternatively, if a two layer optical waveguide is desired the aboveprocess is halted after step (f) is complete.

Additionally, the master used in this embodiment may have a corestructure(s) which are actually bigger than desired in the finalproduct. Such features permit a non-stick coating (e.g., PTFE) or amold-release agent to be applied over the master to help facilitate theremoval of the core structures 60 a and the sub-cladding layer 70 fromthe master 62. Alternatively, separation of the sub-cladding layer fromthe master is facilitated by running cold water over the sub-claddinglayer.

Compared with the clad-first approach, this modified core-first approachalso makes the core structures of waveguides by casting on a master(e.g., Ni or Si) that has no interaction with the liquid core precursor.This modification in the fabrication process permits the completeremoval of the slab region of the core layer and also enables an easyfilling of fine channels by using a low-viscosity core prepolymermixture, which simplifies the production of isolated, buried channelwaveguides. Additionally, the modified core-first method reduces theamount of curing time necessary to produce a waveguide and reduces theamount of evaporation of the liquid core layer during the curing processthereby yielding fully filled buried waveguide structures. Opticalmicrographs of samples of two two-layer waveguide structures made usingthe core-first method (FIG. 7A) and the modified core first method (FIG.7B) confirm that the modified core-first method permits the formation offully filled buried waveguide structures.

Multilayer Cutting Method:

As shown in FIG. 8, a double-layer polymer film 80 containing a thinlayer of core material 82 (e.g., 25 μm) on top of a thick layer 84 ofsub-cladding material (e.g., 100 μm thick) can be easily fabricated in aconventional film casting process. These layers may also be thicker orthinner as is discussed in relation to the thickness of the layers inthe core-first method.

Next, a master 86 having designed features 88 a or 88 b therein is usedto form a modified core layer 82 a or 82 b having openings 90 a or 90 btherein. As shown in FIG. 8, the openings 90 a or 90 b in modified corelayer 82 a or 82 b penetrate through the core layer 82 and into thesub-cladding layer 84. In this method formation of the features in thecore and cladding layers are accomplished by any suitable cuttingtechnique (e.g., hot embossing, diamond cutting, laser ablation orreactive-ion etching (RIE), etc.). After formation of the modified corelayer 82 a or 82 b, a top cladding layer is formed by applying a topcladding material to the double-layer polymer film having modified corelayer 82 a or 82 b with openings 90 a or 90 b formed therein. The topcladding material is cured using any suitable method to yield a topcladding layer 92. During the formation of the top cladding layer 92,the top cladding material fills in the openings 90 a or 90 b so as tocomplete the formation of the buried waveguides 94 a and 94 b.

Buried waveguides 94 a and 94 b contain isolated core structuressandwiched between layers of, or surrounded by, or buried within thesub- and top cladding materials. Such waveguides can be used as basiccomponents of integrated optical circuits in optoelectronic markets.

In another embodiment, a triple layer polymer film (i.e. aclad-core-clad multilayered film) is used to form a waveguide accordingto the method detailed in FIG. 8.

This fabrication approach is also applicable to not only the cyclicolefin monomer compositions discussed herein, but other polymer systemssuch as polyacrylates (such as deuterated polyfluoro-methacrylate),polyimides (such as cross-linked polyimides or fluorinated polyimides),or benzocyclobutene. In addition, other polymers may be used. Thesepolymers include, but are not limited to, heat-curable masspolymerizable materials, photo-curable polymers and solution-basedpolymer materials.

FIGS. 9A to 9D are other examples of waveguides formed using amultilayer cutting method and the above discussed core/cladformulations. FIG. 9A is an optical micrograph of a two-layer isolatedchannel waveguide formed using the multi-layer cutting method; FIG. 9Bdepicts light from a diode laser (λ=820 nm) being applied to the middleisolated channel structure of the waveguide of FIG. 9A; FIG. 9C is athree-layer isolated-buried channel waveguide formed by taking the twoor three layer structure formed by the cutting method and overcoatingthe structure with clad material; and FIG. 9D depicts light from a diodelaser (λ=820 nm) being applied to the middle isolated-buried channelstructure of the waveguide of FIG. 9C. It should be noted that when thephotographs of FIGS. 9B and 9D were taken that the intensity of theinput light from the diode laser is maximized to ascertain if anycross-talk exists between the isolated-buried waveguide structures. Ascan be seen from FIGS. 9B and 9D, the output patterns indicate thatthere is no cross coupling between adjacent waveguide structures.

Although the invention has been shown and described with respect to acertain preferred embodiment or embodiments, it is obvious thatequivalent alterations and modifications will occur to others skilled inthe art upon the reading and understanding of this specification and theannexed drawings. In particular regard to the various functionsperformed by the above described integers (components, assemblies,devices, compositions, etc.), the terms (including a reference to a“means”) used to describe such integers are intended to correspond,unless otherwise indicated, to any integer which performs the specifiedfunction of the described integer (i.e., that is functionallyequivalent), even though not structurally equivalent to the disclosedstructure which performs the function in the herein illustratedexemplary embodiment or embodiments of the invention. In addition, whilea particular feature of the invention may have been described above withrespect to only one of several illustrated embodiments, such feature maybe combined with one or more other features of the other embodiments, asmay be desired and advantageous for any given or particular application.

What is claimed is:
 1. A polycyclic polymer composition formed byaddition polymerization of one or more monomers or oligomers representedby the following structure:

wherein each X′″ independently represents oxygen, nitrogen, sulfur, or amethylene group of the formula —(CH₂)_(n′)— where n′ is an integer of 1to 5; “a” represents a single or double bond; R¹ to R⁴ independentlyrepresent a hydrogen, a hydrocarbyl, or a functional substituent; and mis an integer from 0 to 5, with the proviso that when “a” is a doublebond one of R¹, R² and one of R³, R⁴ are not present.
 2. The polymercomposition of claim 1, provided that when any of R¹ to R⁴ is ahydrocarbyl group, R¹ to R⁴ independently comprises a hydrocarbyl, ahalogenated hydrocarbyl or a perhalogenated hydrocarbyl group which areselected from: i) linear or branched C₁-C₁₀ alkyl groups; ii) linear orbranched C₂-C₁₀ alkenyl groups; iii) linear or branched C₂-C₁₀ alkynylgroups; iv) C₄-C₁₂ cycloalkyl groups; v) C₄-C₁₂ cycloalkenyl groups; vi)C₆-C₁₂ aryl groups; and vii) C₇-C₂₄ aralkyl groups.
 3. The polymercomposition of claim 1, wherein X′″ is nitrogen having a hydrogen or aC₁ to C₁₀ alkyl group.
 4. The polymer composition of claim 1, wherein R¹and R², or R³ and R⁴ are taken together to represent a C₁-C₁₀alkylidenyl group.
 5. The polymer composition of claim 1, wherein one ormore of R¹ to R⁴ represent a functional substituent independentlyselected from —(CH₂)_(n)—CH(CF₃)₂—O—Si(Me)₃,—(CH₂)_(n)—CH(CF₃)₂—O—CH₂—O—CH₃, —(CH₂)_(n)—CH(CF₃)₂—O—C(O)—O—C(CH₃)₃,—(CH₂)_(n)—C(CF₃)₂—OH, —(CH₂)_(n)C(O)NH₂, —(CH₂)_(n)C(O)Cl,—(CH₂)_(n)C(O)OR⁵, —(CH₂)_(n)—OR⁵, —(CH₂)_(n)—OC(O)R⁵,—(CH₂)_(n)—C(O)R⁵, —(CH₂)_(n)—OC(O)OR⁵, —(CH₂)_(n)Si(R⁵)₃,—(CH₂)_(n)Si(OR⁵)₃, —(CH₂)_(n)—O—Si(R⁵)₃, and —(CH₂)_(n)C(O)OR⁶, whereinn independently represents an integer from 0 to 10, R⁵ independentlyrepresents a hydrogen, a linear or branched C₁-C₂₀ alkyl group, a linearor branched C₁-C₂₀ halogenated or perhalogenated alkyl group, a linearor branched C₂-C₁₀ alkenyl group, a linear or branched C₂-C₁₀ alkynylgroup, a C₅-C₁₂ cycloalkyl group, a C₆-C₁₄ aryl group, a C₆-C₁₄halogenated or perhalogenated aryl group, and a C₇-C₂₄ aralkyl group;and R⁶ is selected from —C(CH₃)₃, —Si(CH₃)₃, —CH(R⁷)OCH₂CH₃,—CH(R⁷)OC(CH₃)₃ or one of the following cyclic groups:

or one of the following:

wherein R⁷ represents a hydrogen or a linear or branched (C₁-C₅) alkylgroup.
 6. The polymer composition of claim 4, wherein R⁵ is ahalogenated or perhalogenated group.
 7. The polymer composition of claim1, wherein R¹ and R⁴ are taken together with the two ring carbon atomsto which they are attached to represent a substituted or unsubstitutedcycloaliphatic group containing 4 to 30 ring carbon atoms or asubstituted or unsubstituted aryl group containing 6 to 18 ring carbonatoms or combinations thereof.
 8. The polymer composition of claim 6,wherein the cycloaliphatic group is a monocyclic or polycycliccycloaliphatic group.
 9. The polymer composition of claim 7, wherein thecycloaliphatic group is monounsaturated or multiunsaturated.
 10. Thepolymer composition of claim 1, wherein the composition is ahomopolymer.
 11. The polymer composition of claim 1, wherein thecomposition is a co-polymer comprising at least two different repeatingunits according to the structure of claim
 1. 12. The polymer compositionof claim 1, wherein the number of repeating units in the composition isfrom about 100 to about 100,000.
 13. The polymer composition of claim 1,wherein the number of repeating units in the composition is from about500 to about 50,000.
 14. The polymer composition of claim 1, wherein thenumber of repeating units in the composition is from about 1,000 toabout 10,000.
 15. The polymer composition of claim 1, wherein thepolymer composition is formed from one or more monomers or oligomersaccording to claim 1 in combination with one or more crosslinkingagents.
 16. The polymer composition of claim 15, wherein thecrosslinking agent is selected from at least one of the followingstructures:

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond; a linked multicyclic crosslinking agent as shown inStructure VIII below:

wherein “a” independently represents a single or double bond, mindependently is an integer from 0 to 5, R⁹ is a divalent radicalselected from divalent hydrocarbyl radicals, divalent ether radicals anddivalent silyl radicals, and n is 0 or 1; or a crosslinking agent asshown below:

where n is 1 to
 4. 17. The polymer composition of claim 15, wherein thecrosslinking agent is selected from at least one of the followingstructures:


18. The polymer composition of claim 15, the crosslinking agent isselected from at least one of the following structures:

where m and n, if present, are independently an integer from 1 to
 4. 19.The polymer composition of claim 15, the crosslinking agent is selectedfrom at least one of the following structures:


20. The composition of claim 15, wherein the crosslinking agent is alatent crosslinking agent.
 21. The composition of claim 20, whereinlatent crosslinking agent is selected from one or more of the followingcompounds:

where R_(h) represents a non-halogenated, halogenated or perhalogenatedgroup such as CnQ″_(2n+1), n is an integer from 1 to 10, and Q″represents a hydrogen or a halogen.
 22. A polycyclic polymer compositionformed by addition polymerization of one or more monomers or oligomersrepresented by the following structure:

wherein each X′″ independently represents oxygen, nitrogen, sulfur, or amethylene group of the formula —(CH₂)_(n′)— where n′ is an integer of 1to 5; Q represents an oxygen atom or the group N(R⁸); R⁸ is selectedfrom hydrogen, a halogen, a linear or branched C₁-C₁₀ alkyl, and C₆-C₁₈aryl; and m is an integer from 0 to
 5. 23. The polymer composition ofclaim 22, wherein the composition is a homopolymer.
 24. The polymercomposition of claim 22, wherein the composition is a co-polymer. 25.The polymer composition of claim 22, wherein X′″ is nitrogen having ahydrogen or a C₁ to C₁₀ alkyl group.
 26. The polymer composition ofclaim 22, wherein the number of repeating units in the composition isfrom about 100 to about 100,000.
 27. The polymer composition of claim22, wherein the number of repeating units in the composition is fromabout 500 to about 50,000.
 28. The polymer composition of claim 22,wherein the number of repeating units in the composition is from about1,000 to about 10,000.
 29. The polymer composition of claim 22, whereinthe polymer composition is formed from one or more monomers or oligomersaccording to claim 22 in combination with one or more crosslinkingagents.
 30. The composition of claim 29, wherein the at least onecrosslinking agent is selected from one or more of the followingcompounds:

wherein Y represents a methylene (—CH₂—) group and m independentlyrepresents an integer from 0 to 5, and when m is 0, Y represents asingle bond; a linked multicyclic crosslinking agent as shown inStructure VII below:

wherein “a” independently represents a single or double bond, mindependently is an integer from 0 to 5, R⁹ is a divalent radicalselected from divalent hydrocarbyl radicals, divalent ether radicals anddivalent silyl radicals, and n is 0 or 1; or a crosslinking agent asshown below:

where n is 1 to
 4. 31. The polymer composition of claim 29, wherein theat least one crosslinking agent is selected from one or more of thefollowing compounds:


32. The polymer composition of claim 29, wherein the at least onecrosslinking agent is selected from one or more of the followingcompounds:

where m and n, if present, are independently an integer from 1 to
 4. 33.The ploymer composition of claim 29, wherein the at least onecrosslinking agent is selected from one or more of the followingcompounds


34. The composition of claim 29, wherein the crosslinking agent is alatent crosslinking agent.
 35. The composition of claim 34, whereinlatent crosslinking agent is selected from one or more of the followingcompounds:

where R_(h) represents a non-halogenated, halogenated or perhalogenatedgroup such as CnQ⁴¹ _(2n+1), n is an integer from 1 to 10, and Q″represents a hydrogen or a halogen.
 36. A polycyclic polymer compositionformed by addition polymerization of one or more monomers represented bythe following structure:

wherein X′″ represents oxygen, nitrogen, sulfur, or a methylene group ofthe formula —(CH₂)_(n′)— where n′ is an integer of 1 to 5; R^(D) isdeuterium, “i” is an integer ranging from 0 to 6, with the proviso thatwhen “i” is 0, at least one of R^(1D) and R^(2D) must be present; R¹ andR² independently represent a hydrogen, a hydrocarbyl, or a functionalsubstituent; and R^(1D) and R^(2D), which are optional, independentlyrepresent a deuterium atom or a deuterium enriched hydrocarbyl groupcontaining at least one deuterium atom.
 37. The polymer composition ofclaim 36, wherein X′″ is nitrogen having a hydrogen or a C₁ to C₁₀ alkylgroup.
 38. The polymer composition of claim 36, wherein the number ofrepeating units in the composition is from about 100 to about 100,000.39. The polymer composition of claim 36, wherein the number of repeatingunits in the composition is from about 500 to about 50,000.
 40. Thepolymer composition of claim 36, wherein the number of repeating unitsin the composition is from about 1,000 to about 10,000.
 41. The polymercomposition of claim 36, wherein at least one of R^(1D) and R^(2D) arepresent and R^(1D) and R^(2D) are independently selected from linear orbranched C₁-C₁₀ alkyl, wherein at least 40 percent of the hydrogen atomson the carbon backbone are replaced by deuterium.
 42. The polymercomposition of claim 41, wherein both R^(1D) and R^(2D) are present. 43.The polymer composition of claim 36, wherein at least one of R^(1D) andR^(2D) are present and R^(1D) and R^(2D) are independently selected froma linear or branched C₁-C₁₀ alkyl, wherein at least 50 percent of thehydrogen atoms on the carbon backbone are replaced by deuterium.
 44. Thepolymer composition of claim 43, wherein both R^(1D) and R^(2D) arepresent.
 45. The polymer composition of claim 36, wherein at least oneof R^(1D) and R^(2D) are present and R^(1D) and R^(2D) are independentlyselected from a linear or branched C₁-C₁₀ alkyl, wherein at least 60percent of the hydrogen atoms on the carbon backbone are replaced bydeuterium.
 46. The polymer composition of claim 36, wherein both R^(1D)and R^(2D) are present.
 47. The polymer composition of claim 36, whereinthe polymer composition is formed in combination with at least onecrosslinking agent.
 48. The polymer composition of claim 36, wherein thepolymer composition is formed from a combination of (A) one or moremonomers according to claim 30 with (B) one or more oligomers derivedfrom the monomers of claim
 30. 49. A polymer composition according toclaim 1 for use in waveguides.
 50. A polymer composition according toclaim 22 for use in waveguides.
 51. A polymer composition according toclaim 36 for use in waveguides.